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WO2018235816A1 - Photocurable resin composition, cured coating film, substrate with cured coating film, method for producing same, and virus inactivation method - Google Patents

Photocurable resin composition, cured coating film, substrate with cured coating film, method for producing same, and virus inactivation method Download PDF

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Publication number
WO2018235816A1
WO2018235816A1 PCT/JP2018/023307 JP2018023307W WO2018235816A1 WO 2018235816 A1 WO2018235816 A1 WO 2018235816A1 JP 2018023307 W JP2018023307 W JP 2018023307W WO 2018235816 A1 WO2018235816 A1 WO 2018235816A1
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WO
WIPO (PCT)
Prior art keywords
meth
acrylate
cured film
photocurable resin
resin composition
Prior art date
Application number
PCT/JP2018/023307
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French (fr)
Japanese (ja)
Inventor
保紀 米
佳憲 亀田
Original Assignee
中国塗料株式会社
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Filing date
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Publication of WO2018235816A1 publication Critical patent/WO2018235816A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds

Definitions

  • the present invention relates to a photocurable resin composition, a cured film, a substrate with a cured film, a method for producing them and a method for virus inactivation.
  • influenza virus has become a problem, and since influenza infectious diseases prevail in facilities where many people such as stations, airports, hospitals, and schools come and go, countermeasures are needed. Thus, there is a need for materials that inactivate viruses applicable to these locations.
  • Patent Document 1 discloses an antiviral composition containing silica-coated titanium oxide on which bismuth vanadate is supported and a divalent copper compound.
  • Patent Document 2 discloses an antiviral coating film having a copper-supported oxide, barium sulfate and a water-repellent resin binder.
  • the outstanding antiviral property is called for also in the dark place where light does not reach for a long time.
  • the conventional antiviral compositions and coating films described in Patent Documents 1 and 2 have a problem that antiviral properties are not exhibited in a place where light does not strike for a long time.
  • they since they have heavy metal components that cause metal allergy, they may cause metal allergy when they are in contact with the human body.
  • One embodiment of the present invention provides a photocurable resin composition and the like that can form a cured film having excellent antiviral properties even in a dark place.
  • a substrate with a cured film comprising the substrate and the cured film according to [4] or [5].
  • a method for producing a cured film comprising a curing step of curing the photocurable resin composition according to any one of [1] to [3] by light irradiation. [8] a coating step of coating the photocurable resin composition according to any one of [1] to [3] on at least a part of a substrate; After the application step, a curing step of curing the photocurable resin composition by light irradiation to form a cured film;
  • a method of producing a coated substrate having:
  • a composition having excellent dispersibility of an antiviral agent can be easily obtained, and further, a cured film having excellent antiviral properties can be easily obtained even in a dark place.
  • the photocurable resin composition according to an embodiment of the present invention is selected from polymers containing an alkali metal salt of an acidic group-containing compound and an alkali metal salt of an acidic group-containing compound. Containing an antiviral agent (A) containing at least one of the following, a photocurable resin (B), an unsaturated monomer (C), a pigment (D), and a photopolymerization initiator (E) Do. Since the composition contains such components, it can form a cured film having excellent physical properties, and since it contains the pigment (D), the dispersibility of the antiviral agent (A) is excellent. . Therefore, according to the composition, a cured film excellent in antiviral property can be easily obtained over a long period of time. In addition, since the present composition does not cause metal allergy, a cured film excellent in safety can be easily obtained.
  • the antiviral agent (A) contains at least one selected from polymers containing an alkali metal salt of an acid group-containing compound and an alkali metal salt of an acid group-containing compound. Such an antiviral agent (A) does not cause metal allergy even when in contact with the human body, and is excellent in antiviral properties even in the dark. Moreover, the dispersibility of the antiviral agent (A) in a composition improves by using it with a pigment (D) especially, and the cured film which is more excellent in antiviral property can be obtained.
  • the antiviral agent (A) used in the present composition may be one kind or two or more kinds.
  • the term "antiviral" as used in the present invention means that RNA viruses such as influenza virus have an effect of suppressing infection of a host cell, or suppresses proliferation of the virus in cells after infection of a host cell. Point to the effect.
  • the antiviral agent (A) has antiviral properties against various RNA viruses including influenza virus, but in particular, against influenza virus.
  • the acidic group examples include a sulfonic acid group, a carboxyl group, a phosphoric acid group, etc. From the viewpoint of excellent antiviral property against influenza virus etc., a sulfonic acid group and a carboxyl group are preferable, and a sulfonic acid group is particularly preferable. preferable.
  • the alkali metal is not particularly limited, but is preferably sodium.
  • the alkali metal salt of the acidic group-containing compound has an acidic group capable of binding to the surface protein of the virus or is ionized to have the acidic group.
  • the surface protein of the virus has a role of binding to a sugar chain receptor of the host cell to infect the host, or the virus liberates from the infected cell and spreads the infection to the next cell. By binding to this surface protein, it is believed that these functions are inhibited to exert antiviral properties.
  • the acidic group-containing compound is not particularly limited, and, for example, Sulfonic acids such as alkane sulfonic acid, alkyl benzene sulfonic acid, alkyl phenyl sulfonic acid, alkyl diphenyl ether sulfonic acid, alkyl naphthalene sulfonic acid, modified products of these such as polyoxyethylene; Unsaturated sulfonic acids such as vinyl sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid and styrene sulfonic acid; fatty acid; Aromatic carboxylic acid; (Meth) acrylic acid, (meth) acrylic acid dimer, maleic acid, fumaric acid, vinylbenzoic acid, crotonic acid, itaconic acid, unsaturated carboxylic acids such as citraconic acid; Unsaturated bond-containing phosphoric acids such as 2-hydroxyethyl methacrylate acid phosphate,
  • alkali metal salt of the acidic group-containing compound examples include sodium styrene sulfonate and sodium alkylphenyl sulfonate.
  • the polymer containing the alkali metal salt of the acidic group-containing compound is a homopolymer of a compound having an unsaturated bond among alkali metal salts of the acid group-containing compound, or an alkali metal salt of the acid group-containing compound.
  • Examples thereof include copolymers of a compound having an unsaturated bond and other copolymerizable compounds. These can be obtained by polymerizing by a known method.
  • alkali metals of acid group of homopolymer of acid group-containing compound having unsaturated bond, or copolymer of acid group-containing compound having unsaturated bond and other copolymerizable compound are alkali metal chloride (co (Co) polymer obtained by introducing the above-mentioned acidic group into a polymer or a (co) polymer of the following other copolymerizable compound by a conventionally known method, and further introducing the introduced acidic group into an alkali metal It may be
  • the antiviral agent (A) is a polymer containing an alkali metal salt of an acidic group-containing compound
  • the weight average molecular weight (Mw) of the polymer gives a composition excellent in handleability, and the antiviral property From the viewpoint of being able to easily obtain an excellent cured film, etc., it is preferably at least 5,000, more preferably at least 20,000, further preferably at least 50,000, particularly preferably at least 100,000, preferably at least 5,000,000. More preferably, it is 2 million or less, more preferably 1 million or less.
  • the antiviral agent (A) is a polymer containing an alkali metal salt of an acidic group-containing compound
  • the content of the alkali metal salt of the acidic group-containing compound (alkali metal salt structure of the acidic group-containing compound) is 20 mol% or more is preferable with respect to the said whole polymer from the point that the cured film which is excellent by property can be obtained easily.
  • the acid group is a sulfonic acid group
  • the content of the alkali metal salt of the sulfonic acid group-containing compound (alkali metal salt structure of the sulfonic acid group-containing compound) falls within the above range, the cured film becomes moisture Even in the case of contact with the above, whitening of the film can be suppressed.
  • the antiviral agent (A) is a polymer containing an alkali metal salt of an acidic group-containing compound
  • the acidic group in the molecule (acidic group in the molecule and the salt group of the acidic group (salt)
  • the ratio of the acid group regarded as a salt among the total of the acid groups) maintains the acidity of the present composition in an appropriate range, and from the viewpoint of being able to easily obtain a composition which is more excellent in stability, etc. It is preferably 50 mol% or more, more preferably 70 to 100 mol%, and particularly preferably 85 to 100 mol%.
  • the polymer containing the alkali metal salt of the acid group-containing compound and the alkali metal salt of the acid group-containing compound is further crosslinked by a crosslinking agent from the viewpoint that an antiviral agent (A) excellent in water resistance can be obtained.
  • a crosslinking agent include epoxy compounds, glycidyl compounds, aziridine compounds, oxazoline compounds, amine compounds, polyaminoamide compounds, imidazole compounds, hydrazide compounds, melamine compounds, acid anhydrides, phenol compounds, heat latent cationic polymerization catalysts, and photolattices.
  • the antiviral agent (A) is a particulate antiviral agent immobilized on an inorganic carrier such as talc, bentonite, clay, kaolin, diatomaceous earth, silica, vermiculite, perlite, or an organic polymer carrier such as polyethylene or polypropylene. May be
  • an inorganic carrier such as talc, bentonite, clay, kaolin, diatomaceous earth, silica, vermiculite, perlite, or an organic polymer carrier such as polyethylene or polypropylene.
  • the average particle diameter of the particulate antiviral agent (A) measured by the laser diffraction particle size distribution measuring device is preferably 0.5, from the viewpoint of easily obtaining a cured film which is more excellent in antiviral property. It is -30 ⁇ m, more preferably 1-25 ⁇ m. In addition, the said average particle diameter points out the particle size (what is called median diameter D50) of 50% of accumulation in the particle size distribution on a volume basis.
  • the antiviral agent (A) having an average particle diameter in the above range is unlikely to be detached from the cured film, and therefore, a cured film can be obtained which is more excellent in antiviral persistence.
  • the antiviral agent (A) when an antiviral agent (A) having an average particle diameter larger than that of the pigment (D) is used, the antiviral agent (A) is oriented on the surface of the cured film to obtain a cured film having more excellent antiviral properties. it can.
  • the antiviral agent (A) may be used in the form of a dispersion dispersed by a dispersion medium.
  • the dispersion medium is not particularly limited, and conventionally known dispersion media such as water and organic solvents can be used, and as the organic solvent, aromatic hydrocarbons (eg, xylene, toluene), ketones (eg, ketones) Examples: methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, esters (eg: ethyl acetate, butyl acetate, isobutyl acetate), alcohols (eg: isopropyl alcohol, butanol), glycol ethers (eg: propylene glycol monomethyl ether), etc. It can be mentioned.
  • the compounding quantity of the antiviral agent (A) with respect to solid content of 100% by mass of the present composition is preferably 0 in terms of being able to obtain a cured film which is more excellent in antiviral property and further excellent in hardness and water resistance.
  • the content is preferably 5 to 15% by mass, more preferably 1 to 10% by mass, and particularly preferably 2 to 5% by mass. If the compounding amount is less than the above range, the resulting cured film may not exhibit sufficient antiviral properties, and if the compounding amount exceeds the above range, the hardness or water resistance of the cured film may be reduced. .
  • the photocurable resin (B) is not particularly limited as long as it is a photocurable resin other than a polymer containing an alkali metal salt of an acidic group-containing compound, but as the photocurable resin (B), for example, And oligomers and polymers having at least one unsaturated double bond.
  • the resin (B) used in the present composition may be one kind or two or more kinds.
  • Examples of the unsaturated double bond include a (meth) acryloyl group, a vinyl group, an allyl group and a styryl group, and a (meth) acryloyl group is preferable from the viewpoint of reactivity at the time of active energy ray irradiation.
  • Examples of the resin (B) include polyester (meth) acrylate resins, epoxy (meth) acrylate resins, polyether (meth) acrylate resins and urethane (meth) acrylate resins.
  • polyester (meth) acrylate resin for example, polyester (meth) acrylate resin obtained by reacting (meth) acrylic acid with polyester synthesized from polybasic acid or its anhydride and polyhydric alcohol It can be mentioned.
  • the polybasic acids include phthalic acid, succinic acid, adipic acid, glutaric acid, sebacic acid, isoecebacic acid, tetrahydrophthalic acid, hexahydrophthalic acid, dimer acid, trimellitic acid, pyromellitic acid, pimelic acid, And azelaic acid.
  • polyhydric alcohol examples include 1,6-hexanediol, diethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, neopentyl glycol, dipropylene glycol, polyethylene glycol and polypropylene glycol.
  • epoxy (meth) acrylate resins examples include (meth) acrylic acid-modified epoxy resins obtained by adding (meth) acrylic acid to epoxy resins.
  • the epoxy resin to be subjected to modification for example, a resin obtained by reacting bisphenol A, bisphenol F, bisphenol S or phenol novolac with epichlorohydrin, cyclopentadiene oxide or cyclohexene oxide and epichlorohydrin are reacted with each other. The obtained resin is mentioned.
  • polyether (meth) acrylate resins examples include polyether (meth) acrylate resins obtained by transesterification of polyether and (meth) acrylic acid ester such as ethyl (meth) acrylate.
  • polyether examples include polyethers obtained by ethoxylation or propoxylation of trimethylolpropane and pentaerythritol and the like, and polyethers obtained by polyetherifying 1,4-butanediol and the like. Can be mentioned.
  • urethane (meth) acrylate resins include urethane (meth) acrylate resins obtained by reacting an isocyanate compound, a hydroxy group-containing (meth) acrylate compound, and optionally a polyol compound.
  • the isocyanate compound include tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate.
  • Examples of the hydroxy group-containing (meth) acrylate compound include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4- Examples thereof include hydroxyl group-containing alkyl esters of (meth) acrylic acid such as hydroxybutyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate.
  • Examples of the polyol compound include an adduct of hydrogenated bisphenol A and ethylene oxide, hydrogenated bisphenol A, neopentyl glycol, 1,6-hexanediol, and trimethylolpropane.
  • the compounding amount of the resin (B) relative to 100% by mass of the solid content of the present composition can easily obtain a cured film excellent in hardness and scratch resistance, and can suppress curing shrinkage when forming the cured film, etc. It is preferably 3 to 30% by mass, more preferably 5 to 25% by mass, and particularly preferably 10 to 20% by mass. If the amount is less than the above range, the hardness and the scratch resistance of the resulting cured film may be reduced. If the amount is more than the range, the cure shrinkage upon forming the cured film may be too large. There is.
  • Unsaturated Monomer (C)> As unsaturated monomer (C), monofunctional monomer having one unsaturated double bond, bifunctional monomer having two unsaturated double bonds, trifunctional or more having three or more unsaturated double bonds And polyfunctional monomers. Among these monomers, (meth) acrylate monomers are preferable from the viewpoint of being able to easily obtain a cured film which is more excellent in photocurability and excellent in antiviral property.
  • the unsaturated monomer (C) used in the present composition may be of one type or two or more types, and using at least one of a monofunctional monomer and a bifunctional monomer is low in viscosity and excellent in coating workability. It is preferable from the point that this composition can be obtained easily.
  • Examples of monofunctional monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) Acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 3,5,5-trimethylhexyl (meth) ) Acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, isomyristyl (meth) acrylate, al
  • bifunctional monomer for example, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, PEG200 # di (meth) acrylate (EO part is n ⁇ 4), tetraethylene glycol di (meth) acrylate, PEG300 # Di (meth) acrylate (EO part n 6 6), PEG 400 # di (meth) acrylate (EO part n 9 9), PEG 600 # di (meth) acrylate (EO part n 13 14), polyethylene Glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, PO-added neopentyl glycol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) Acrylate, hydroxide Pivalate neopentyl glycol di (meth) acrylate, polytet
  • the compounding quantity of the unsaturated monomer (C) with respect to solid content 100 mass% of this composition can obtain easily the composition which is excellent in coating property, and can suppress the curing defect at the time of forming a cured film.
  • the amount is preferably 40 to 90% by mass, more preferably 45 to 85% by mass, and particularly preferably 50 to 80% by mass from the viewpoint that a cured film having a desired hardness can be easily obtained. If the compounding amount is less than the above range, the viscosity of the composition obtained may be increased and the coatability may be reduced, and if the compounding amount exceeds the above range, the hardness of the cured film is reduced or a cured film is formed. Poor curing may occur.
  • the blending ratio of the photocurable resin (B) to the unsaturated monomer (C) is 20% by mass or less of the component (B) based on 100% by mass in total of the component (B) and the component (C) It is preferable from the point that the cured film which is more excellent in antiviral property is obtained.
  • the pigment (D) As the pigment (D), conventionally known pigments can be used.
  • the pigment (D) is particles other than the components (A) to (C) and (E). Since this composition uses a pigment (D), a cured film having irregularities on the surface can be obtained, and it is considered that the area in which the antiviral agent (A) and the virus are in contact is increased. Furthermore, it is considered that the dispersibility of the antiviral agent (A) can be improved and it can be uniformly oriented on the surface of the cured film. For this reason, the cured film which is excellent in antiviral property can be obtained easily.
  • the pigment (D) used in the present composition may be one kind or two or more kinds.
  • organic resin particles such as acrylic particles, polystyrene particles, polyethylene wax particles, polypropylene wax particles, PTFE particles, urethane particles, silicone particles, metal oxide particles (eg, silica particles, Inorganic fine particles such as aluminum oxide fine particles, zirconium oxide fine particles, zinc oxide fine particles, titanium oxide fine particles) can be mentioned.
  • metal oxide particles eg, silica particles, Inorganic fine particles such as aluminum oxide fine particles, zirconium oxide fine particles, zinc oxide fine particles, titanium oxide fine particles
  • inorganic fine particles are preferable, silica Microparticles are more preferred.
  • the average particle size of the pigment (D) is not particularly limited, but preferably 1 to 10 ⁇ m, more preferably 2 to 8 ⁇ m.
  • the average particle diameter refers to the cumulative 50% particle diameter (so-called median diameter D50) in the volume-based particle size distribution, and can be measured by a laser diffraction particle size distribution measuring device.
  • the lower limit of the pigment volume concentration (hereinafter also referred to as "PVC") of the pigment (D) is preferably 2%, more preferably 3%, particularly preferably 5%.
  • the upper limit is preferably 25%, more preferably 20%, particularly preferably 15%.
  • Said PVC refers to the total volume concentration of the pigment (D) with respect to the volume of solids in the present composition. Specifically, it can be obtained from the following equation.
  • PVC volume of pigment (D) ⁇ 100 / volume of solid content in the composition
  • the solid content is a component obtained by removing volatile components such as an organic solvent from the composition, and curing The component which remains as a cured film is shown.
  • the volume of solid content in the present composition can be calculated from the mass and the true density of the solid content of the composition.
  • the mass and the true density of the solid content may be measured values or values calculated from raw materials used.
  • the volume of the pigment (D) can be calculated from the mass and the true density of the pigment (D) used.
  • the mass and the true density of the pigment (D) may be measured values or values calculated from the raw materials used. For example, it can be calculated by separating the pigment (D) and the other components from the solid content of the present composition, and measuring the mass and true density of the separated pigment (D).
  • the photopolymerization initiator (E) is not particularly limited as long as it is a compound that can generate a radical or a cation upon irradiation with light and react the above components (B) and (C) to cure the present composition.
  • the initiator (E) used in the present composition may be one kind or two or more kinds.
  • an alkyl phenone type initiator As an initiator (E), an alkyl phenone type initiator, an acyl phosphine oxide type initiator, and a hydrogen abstraction type initiator are mentioned, for example.
  • alkyl phenone type initiator for example, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane -1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- ⁇ 4- [4- (2 -Hydroxy-2-methyl-propionyl) -benzyl] phenyl ⁇ -2-methyl-propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl 1- [4- (4-morpholinyl) phenyl] -1-butanone.
  • acylphosphine oxide initiator examples include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.
  • hydrogen abstraction initiators examples include benzophenone, 2,4,6-trimethylbenzophenone, methyl benzoylbenzoate, 2,4-diethylthioxanthone, 2-ethylanthraquinone, camphorquinone, oxy-phenyl-acetic acid 2- Mixtures of [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester and oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester, including phenylglyoxylic acid methyl ester .
  • 1-hydroxy-cyclohexyl-phenyl-ketone and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide are preferable.
  • the content of the initiator (E) based on 100% by mass of the solid content of the present composition can easily obtain a cured film which is excellent in curability, hardness and adhesion with a substrate, and further yellowing due to ultraviolet light etc.
  • the content is 0.1 to 10% by mass, more preferably 3 to 9% by mass, and particularly preferably 4 to 8% by mass, from the viewpoint of easily obtaining a cured film capable of suppressing the above. If the compounding amount is less than the above range, the curability at the time of forming a cured film may be insufficient, and the hardness of the obtained cured film may be reduced.
  • the compounding amount exceeds the above range, the unreacted initiator (E) tends to remain in the cured film, the hardness of the obtained cured film tends to decrease, and the cured film is easily yellowed by ultraviolet light and the like. In addition, the adhesion to the substrate may be reduced.
  • additives other than the components described above may be added to the composition.
  • additives generally used in the field of the present invention can be used in the range not to impair the effects of the present invention, for example, organic solvents, leveling agents, antifoaming agents, polymerization inhibitors, Non-reactive diluents, matting agents, anti-settling agents, dispersing agents, heat stabilizers, UV absorbers may be mentioned. These compounding quantities can be suitably adjusted in the range which does not impair the effect of this invention.
  • the other additives may be used alone or in combination of two or more.
  • the composition may contain an organic solvent from the viewpoint of adjusting the viscosity to a predetermined range.
  • organic solvent conventionally known solvents can be used.
  • aromatic hydrocarbons eg: xylene, toluene
  • ketones eg: methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone
  • esters eg: ethyl acetate, butyl acetate, isobutyl acetate
  • alcohols eg: isopropyl Alcohol, butanol
  • glycol ethers eg, propylene glycol monomethyl ether
  • a leveling agent is blended from the viewpoint of improving the repelling of the composition, improving the wettability to the substrate surface, and easily forming a cured film having a uniform film thickness.
  • a leveling agent various leveling agents, such as fluorine type, an acryl type, and silicon type, are mentioned, for example.
  • the compounding amount of the leveling agent with respect to 100% by mass of the solid content of the present composition is preferably 0.1 to 1.5% by mass, more preferably 0.2 to 1.0% by mass.
  • an antifoaming agent it is preferable to add an antifoaming agent to the present composition from the viewpoint of suppressing the generation of air bubbles in the composition and easily forming a cured film having a good appearance.
  • an antifoamer various antifoamers, such as an acryl type and a silicon type, are mentioned, for example.
  • the compounding amount of the antifoaming agent with respect to 100% by mass of the solid content of the present composition is preferably 0.0001 to 1.0% by mass.
  • a dispersing agent may be added to the present composition from the viewpoint of improving the dispersibility of the pigment (D) in the composition and easily forming a cured film having a good appearance.
  • the dispersant is not particularly limited, and, for example, a copolymer having a pigment-adsorbing group such as carboxylic acid, phosphoric acid or amine, a copolymer having a compatible chain such as fatty acid, polyamino, polyether, polyester, polyurethane or polyacrylate Various dispersants such as copolymers may be mentioned.
  • the compounding amount of the dispersant based on 100% by mass of the solid content of the present composition is preferably 0.1 to 10% by mass.
  • the cured film formed using this composition is excellent in antiviral property and does not cause metal allergy, so it is in contact with human beings (eg, portable) Devices equipped with image display devices such as telephones, smartphones and tablets, electrical appliances such as home appliances, protective films for image display devices, furniture, doorknobs, handrails, handlebars of automobiles, toys)
  • image display devices such as telephones, smartphones and tablets
  • electrical appliances such as home appliances
  • protective films for image display devices furniture, doorknobs, handrails, handlebars of automobiles, toys
  • the cured film (hereinafter also referred to as "the main cured film") according to an embodiment of the present invention is a film formed from the present composition, and specifically, the step of curing the present composition by light irradiation It can manufacture by including (hardening process).
  • the base material with a cured film which concerns on one Embodiment of this invention contains a base material and the said main cured film.
  • the present cured film and the substrate with the present cured film specifically apply the present composition to at least a part of the substrate (coating step) and then apply the present composition by light irradiation. It can manufacture by including the process (hardening process) made to harden
  • the substrate is not particularly limited as long as it is a substrate on which the main cured film is to be formed, and examples thereof include plastics, woods, metals, glasses, ceramics, and concrete.
  • the plastic include various plastic substrates (eg, triacetyl cellulose, polyethylene terephthalate (PET), diacetyl cellulose, acetate butyrate cellulose, polyether sulfone, polyacrylic, polyurethane, polyester, polycarbonate, polysulfone, polyether, Films and molded articles formed from polymethylpentene, polyether ketone, (meth) acrylonitrile and the like can be mentioned.
  • PET polyethylene terephthalate
  • diacetyl cellulose acetate butyrate cellulose
  • polyether sulfone polyacrylic, polyurethane
  • polyester polycarbonate
  • polysulfone polyether
  • the application (coating) method in the application step may be appropriately selected according to the composition of the present composition to be used, the type of the substrate, etc.
  • spray coating, dip coating, air knife coating, curtain Coating method, roller coating method, wire bar coating method, gravure coating method, extrusion coating method, dipping method can be mentioned.
  • a drying step may be provided to dry the applied composition before the curing step. This drying step may be performed under heating at about 5 to 120 ° C. to shorten the drying time.
  • the light irradiated in the curing step is preferably an active energy ray
  • the active energy ray include far ultraviolet rays, ultraviolet rays, near ultraviolet rays, rays such as infrared rays, electromagnetic waves such as X rays and ⁇ rays, and electron rays And a proton beam and a neutron beam.
  • ultraviolet rays are preferable in view of curing speed, availability of an irradiation apparatus, cost and the like.
  • the irradiation dose of ultraviolet light is 100 to 3, using a high pressure mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrode lamp, an LED lamp or the like that emits light in a wavelength range of 200 to 500 nm.
  • the method etc. which are irradiated by about 000 mJ / cm ⁇ 2 > etc. are mentioned.
  • heating may be performed at about 5 to 120 ° C. in order to shorten the curing time after or during the light irradiation.
  • the thickness of the cured film is not particularly limited as long as it can protect the substrate, but it is preferably 1 to 10 ⁇ m, more preferably 2 to 7 ⁇ m, and particularly preferably 2 to 5 ⁇ m.
  • the average length (RSm) of the roughness curvilinear element measured based on JIS B 0601: 2013 of the main cured film surface is preferably 300 ⁇ m or less. If the RSm is 300 ⁇ m or less, a cured film which is more excellent in antiviral property tends to be obtained.
  • the virus inactivation method according to an embodiment of the present invention is a method of inactivating a virus at least in a dark place using the main cured film or the substrate with the main cured film. It is. Specifically, the virus is inactivated by bringing the cured film into contact with the virus. The contact is usually performed at normal temperature, but may be performed under heating in some cases. Specifically, for articles such as housings of home appliances, image display devices such as displays of smartphones and protective films, interiors of automobiles, window films of automobiles, interior materials such as walls, floors and ceilings, surfaces of furniture, etc.
  • the method of forming this cured film and inactivating the virus which contacted the cured film is mentioned.
  • the virus can be inactivated even when these articles are in a dark place such as in a room, in a garage, in storage furniture and in a bag or at night.
  • This method can be used for inactivation of various RNA viruses including influenza virus, and in particular, can be preferably used for inactivation of influenza virus. Whether or not the virus has been inactivated can be confirmed by the value of the virus activity value in accordance with JIS L 1922: 2016.
  • the "dark place" refers to a place where no light exists, including ultraviolet light.
  • a photocurable resin composition was prepared by mixing the following materials in the composition shown in Table 1.
  • the numerical value of the column of the photocurable resin composition in Table 1 shows a mass part, and the density of solid content and solid content is the value computed from the used raw material.
  • ⁇ Antiviral agent (A)> Water dispersion containing sodium salt of acid group-containing polymer and sodium alkylphenyl sulfonate (solid content 35%)
  • ⁇ Preparation of a substrate with a cured film> The photocurable resin composition prepared above is applied once to a PET film “Cosmo Shine A4300” manufactured by Toyobo Co., Ltd. so that the dry film thickness is about 3 ⁇ m, and the ultraviolet light is irradiated with a high pressure mercury lamp. (Irradiation dose: 400 mJ / cm 2 ), the coating was cured to obtain a substrate with a cured coating.
  • Virus activity value of the substrate with a cured film obtained (antiviral) in accordance with JIS L 1922: 2016 except that the following concentration of influenza virus solution was used to wash out on a petri dish and recovery of the washout solution was performed was evaluated. Specifically, a substrate with a cured film and a substrate without a cured film (control sample) are cut into 6 cm square and used as a sample, and the sample is placed in a petri dish, and influenza virus liquid (concentration: 10 5 to 10) on the surface 6 PFU / mL) was added dropwise (reaction area 4 cm square), and allowed to stand in the dark (25 ° C.) for 2 hours.
  • influenza virus liquid concentration: 10 5 to 10
  • the virus solution was washed out on a petri dish and recovered by the solution to prepare a dilution series.
  • Epithelial cells dog kidney-derived cells
  • the virus infectivity titer was measured by TCID 50 assay to determine the antiviral activity value. Those having an antiviral activity value of 2.0 or more were taken as pass, and those having 3.0 or more were evaluated as particularly excellent. The results are shown in Table 1.

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Abstract

The present invention relates to a photocurable resin composition, a cured coating film, a substrate with a cured coating film, a method for producing the same, and a virus inactivation method. The photocurable resin composition comprises: (A) an antiviral agent containing at least one selected from an alkali metal salt of an acid group-containing compound, and a polymer containing an alkali metal salt of an acid group-containing compound; (B) a photocurable resin, (C) an unsaturated monomer, (D) a pigment, and (E) a photopolymerization initiator.

Description

光硬化性樹脂組成物、硬化被膜、硬化被膜付き基材、これらの製造方法およびウイルス不活化方法Photocurable resin composition, cured film, substrate with cured film, method for producing them and method for virus inactivation
　本発明は、光硬化性樹脂組成物、硬化被膜、硬化被膜付き基材、これらの製造方法およびウイルス不活化方法に関する。 The present invention relates to a photocurable resin composition, a cured film, a substrate with a cured film, a method for producing them and a method for virus inactivation.
　近年、インフルエンザウイルスの流行が問題となっており、駅、空港、病院、学校等の多くの人が行き交う施設等においてインフルエンザ感染症が流行することから、対応策が必要とされている。よって、これらの場所に適用可能なウイルスを不活化する材料が求められている。 In recent years, the epidemic of influenza virus has become a problem, and since influenza infectious diseases prevail in facilities where many people such as stations, airports, hospitals, and schools come and go, countermeasures are needed. Thus, there is a need for materials that inactivate viruses applicable to these locations.
　このような材料として、例えば、特許文献１には、バナジン酸ビスマスが担持されたシリカ被膜酸化チタンと、２価銅化合物とを含有する抗ウイルス性組成物が開示されている。
　また、特許文献２には、銅担持酸化物、硫酸バリウムおよび撥水性の樹脂バインダーを有する抗ウイルス性塗膜が開示されている。 As such a material, for example, Patent Document 1 discloses an antiviral composition containing silica-coated titanium oxide on which bismuth vanadate is supported and a divalent copper compound.
Patent Document 2 discloses an antiviral coating film having a copper-supported oxide, barium sulfate and a water-repellent resin binder.
特開２０１６－１１３４１７号公報JP, 2016-113417, A 特開２０１５－２０５９９８号公報JP, 2015-205998, A
　前記施設等では、光が長時間当たらない暗所においても優れた抗ウイルス性が求められている。
　しかしながら、前記特許文献１や２に記載の従来の抗ウイルス組成物および塗膜は、光が長時間当たらない場所では抗ウイルス性が発揮されないという問題があった。また、これらは金属アレルギーの原因となる重金属成分を有しているため、人体に触れると金属アレルギーを引き起こす場合があった。 In the above-mentioned facilities etc., the outstanding antiviral property is called for also in the dark place where light does not reach for a long time.
However, the conventional antiviral compositions and coating films described in Patent Documents 1 and 2 have a problem that antiviral properties are not exhibited in a place where light does not strike for a long time. In addition, since they have heavy metal components that cause metal allergy, they may cause metal allergy when they are in contact with the human body.
　本発明の一実施形態は、暗所においても抗ウイルス性に優れる硬化被膜を形成できる光硬化性樹脂組成物等を提供する。 One embodiment of the present invention provides a photocurable resin composition and the like that can form a cured film having excellent antiviral properties even in a dark place.
　本発明者らが、前記課題を解決する方法について鋭意検討を重ねた結果、特定の組成物によれば、前記課題を解決できることを見出し、本発明を完成するに至った。
　本発明の構成例は以下の通りである。 As a result of extensive investigations by the present inventors about methods for solving the problems, the present inventors have found that the problems can be solved according to a specific composition, and have completed the present invention.
The structural example of this invention is as follows.
　［１］　酸性基含有化合物のアルカリ金属塩および酸性基含有化合物のアルカリ金属塩を含む重合体から選択される少なくとも１種を含む抗ウイルス剤（Ａ）と、光硬化性樹脂（Ｂ）と、不飽和単量体（Ｃ）と、顔料（Ｄ）と、光重合開始剤（Ｅ）とを含有する光硬化性樹脂組成物。 [1] An antiviral agent (A) containing at least one selected from a polymer containing an alkali metal salt of an acid group-containing compound and an alkali metal salt of an acid group-containing compound, and a photocurable resin (B) The photocurable resin composition containing an unsaturated monomer (C), a pigment (D), and a photoinitiator (E).
　［２］　前記顔料（Ｄ）が無機顔料を含有する、［１］に記載の光硬化性樹脂組成物。 [2] The photocurable resin composition according to [1], wherein the pigment (D) contains an inorganic pigment.
　［３］　前記顔料（Ｄ）の顔料容積濃度（ＰＶＣ）が２％以上である、［１］または［２］に記載の光硬化性樹脂組成物。 [3] The photocurable resin composition according to [1] or [2], wherein the pigment volume concentration (PVC) of the pigment (D) is 2% or more.
　［４］　［１］～［３］のいずれかに記載の光硬化性樹脂組成物から形成された硬化被膜。
　［５］　前記硬化被膜の、ＪＩＳ　Ｂ　０６０１：２０１３に基づいて測定した粗さ曲線要素の平均長さ（ＲＳｍ）が３００μｍ以下である、［４］に記載の硬化被膜。 [4] A cured film formed from the photocurable resin composition according to any one of [1] to [3].
[5] The cured film according to [4], wherein an average length (RSm) of a roughness curvilinear element measured based on JIS B 0601: 2013 of the cured film is 300 μm or less.
　［６］　基材と［４］または［５］に記載の硬化被膜とを含む硬化被膜付き基材。 [6] A substrate with a cured film comprising the substrate and the cured film according to [4] or [5].
　［７］　［１］～［３］のいずれかに記載の光硬化性樹脂組成物を光照射により硬化させる硬化工程を有する硬化被膜の製造方法。
　［８］　［１］～［３］のいずれかに記載の光硬化性樹脂組成物を基材の少なくとも一部に塗布する塗布工程と、
　前記塗布工程の後、光照射により前記光硬化性樹脂組成物を硬化させて硬化被膜を形成する硬化工程と、
を有する被膜付き基材の製造方法。 [7] A method for producing a cured film, comprising a curing step of curing the photocurable resin composition according to any one of [1] to [3] by light irradiation.
[8] a coating step of coating the photocurable resin composition according to any one of [1] to [3] on at least a part of a substrate;
After the application step, a curing step of curing the photocurable resin composition by light irradiation to form a cured film;
A method of producing a coated substrate having:
　［９］　［４］もしくは［５］に記載の硬化被膜、または、［６］に記載の硬化被膜付き基材を用いて、少なくとも暗所においてウイルスを不活化するウイルス不活化方法。 [9] A virus inactivation method of inactivating a virus at least in the dark using the cured film according to [4] or [5] or the substrate with a cured film according to [6].
　本発明の一実施形態によれば、抗ウイルス剤の分散性に優れる組成物を容易に得ることができ、さらに暗所においても抗ウイルス性に優れる硬化被膜を容易に得ることができる。 According to one embodiment of the present invention, a composition having excellent dispersibility of an antiviral agent can be easily obtained, and further, a cured film having excellent antiviral properties can be easily obtained even in a dark place.
≪光硬化性樹脂組成物≫
　本発明の一実施形態に係る光硬化性樹脂組成物（以下「本組成物」ともいう。）は、酸性基含有化合物のアルカリ金属塩および酸性基含有化合物のアルカリ金属塩を含む重合体から選択される少なくとも１種を含む抗ウイルス剤（Ａ）と、光硬化性樹脂（Ｂ）と、不飽和単量体（Ｃ）と、顔料（Ｄ）と、光重合開始剤（Ｅ）とを含有する。
　本組成物は、このような各成分を含有するため、優れた物性を有する硬化被膜を形成することができ、かつ顔料（Ｄ）を含有するため、抗ウイルス剤（Ａ）の分散性に優れる。このため、該組成物によれば、長期に亘って、抗ウイルス性に優れる硬化被膜を容易に得ることができる。また、本組成物は、金属アレルギーを引き起こさないため、安全性に優れる硬化被膜を容易に得ることができる。 «Photo-curable resin composition»
The photocurable resin composition according to an embodiment of the present invention (hereinafter also referred to as "the present composition") is selected from polymers containing an alkali metal salt of an acidic group-containing compound and an alkali metal salt of an acidic group-containing compound. Containing an antiviral agent (A) containing at least one of the following, a photocurable resin (B), an unsaturated monomer (C), a pigment (D), and a photopolymerization initiator (E) Do.
Since the composition contains such components, it can form a cured film having excellent physical properties, and since it contains the pigment (D), the dispersibility of the antiviral agent (A) is excellent. . Therefore, according to the composition, a cured film excellent in antiviral property can be easily obtained over a long period of time. In addition, since the present composition does not cause metal allergy, a cured film excellent in safety can be easily obtained.
＜抗ウイルス剤（Ａ）＞
　前記抗ウイルス剤（Ａ）は、酸性基含有化合物のアルカリ金属塩および酸性基含有化合物のアルカリ金属塩を含む重合体から選択される少なくとも１種を含む。
　このような抗ウイルス剤（Ａ）は、人体と接触しても金属アレルギーを引き起こさず、暗所においても抗ウイルス性に優れる。また、特に、顔料（Ｄ）とともに用いることで、組成物中における抗ウイルス剤（Ａ）の分散性が向上し、より抗ウイルス性に優れる硬化被膜を得ることができる。
　本組成物に用いられる抗ウイルス剤（Ａ）は、１種でも２種以上でもよい。
　なお、本発明でいう「抗ウイルス性」とは、インフルエンザウイルス等のＲＮＡウイルスが、宿主細胞に感染することを抑制する効果、または宿主細胞に感染した後、細胞中で増殖することを抑制する効果を指す。 <Antiviral agent (A)>
The antiviral agent (A) contains at least one selected from polymers containing an alkali metal salt of an acid group-containing compound and an alkali metal salt of an acid group-containing compound.
Such an antiviral agent (A) does not cause metal allergy even when in contact with the human body, and is excellent in antiviral properties even in the dark. Moreover, the dispersibility of the antiviral agent (A) in a composition improves by using it with a pigment (D) especially, and the cured film which is more excellent in antiviral property can be obtained.
The antiviral agent (A) used in the present composition may be one kind or two or more kinds.
The term "antiviral" as used in the present invention means that RNA viruses such as influenza virus have an effect of suppressing infection of a host cell, or suppresses proliferation of the virus in cells after infection of a host cell. Point to the effect.
　抗ウイルス剤（Ａ）は、インフルエンザウイルスを含む様々なＲＮＡウイルスに対し抗ウイルス性を有するが、特に、インフルエンザウイルスに対し抗ウイルス性を有する。 The antiviral agent (A) has antiviral properties against various RNA viruses including influenza virus, but in particular, against influenza virus.
　前記酸性基としては、例えば、スルホン酸基、カルボキシル基、リン酸基等が挙げられ、インフルエンザウイルスに対する抗ウイルス性に優れる等の点から、スルホン酸基およびカルボキシル基が好ましく、スルホン酸基が特に好ましい。
　前記アルカリ金属としては特に制限されないが、ナトリウムが好ましい。 Examples of the acidic group include a sulfonic acid group, a carboxyl group, a phosphoric acid group, etc. From the viewpoint of excellent antiviral property against influenza virus etc., a sulfonic acid group and a carboxyl group are preferable, and a sulfonic acid group is particularly preferable. preferable.
The alkali metal is not particularly limited, but is preferably sodium.
＜酸性基含有化合物のアルカリ金属塩＞
　酸性基含有化合物のアルカリ金属塩は、ウイルスの表面タンパク質に結合可能な酸性基を有しているかまたは電離して該酸性基を有する状態になる。ウイルスの表面タンパク質は、宿主細胞の糖鎖受容体に結合して宿主に感染したり、ウイルスが感染細胞から遊離して次の細胞へ感染拡大する役割を有しているが、前記酸性基がこの表面タンパク質に結合することで、これらの働きを阻害して、抗ウイルス性を発揮すると考えられる。 <Alkali metal salt of acid group-containing compound>
The alkali metal salt of the acidic group-containing compound has an acidic group capable of binding to the surface protein of the virus or is ionized to have the acidic group. The surface protein of the virus has a role of binding to a sugar chain receptor of the host cell to infect the host, or the virus liberates from the infected cell and spreads the infection to the next cell. By binding to this surface protein, it is believed that these functions are inhibited to exert antiviral properties.
　前記酸性基含有化合物としては特に限定されないが、例えば、
　アルカンスルホン酸、アルキルベンゼンスルホン酸、アルキルフェニルスルホン酸、アルキルジフェニルエーテルスルホン酸、アルキルナフタレンスルホン酸、これらのポリオキシエチレン等の変性物などのスルホン酸類；
　ビニルスルホン酸、アリルスルホン酸、メタリルスルホン酸、スチレンスルホン酸などの不飽和スルホン酸類；
　脂肪酸；
　芳香族カルボン酸；
　（メタ）アクリル酸、（メタ）アクリル酸ダイマー、マレイン酸、フマル酸、ビニル安息香酸、クロトン酸、イタコン酸、シトラコン酸等の不飽和カルボン酸；
　２－ヒドロキシエチルメタクリレートアシッドホスフェート、２－アクリロイルオキシエチルアシッドホスフェート、ビス（２－メタクリロイルオキシエチル）ホスフェート、ビス（２－アクリロイルオキシエチル）ホスフェートなどの不飽和結合含有リン酸類；
が挙げられる。
　これらの化合物は、置換基として、アルキル基、アリール基等の有機基を有していてもよく、エステル化体等の誘導体であってもよい。 The acidic group-containing compound is not particularly limited, and, for example,
Sulfonic acids such as alkane sulfonic acid, alkyl benzene sulfonic acid, alkyl phenyl sulfonic acid, alkyl diphenyl ether sulfonic acid, alkyl naphthalene sulfonic acid, modified products of these such as polyoxyethylene;
Unsaturated sulfonic acids such as vinyl sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid and styrene sulfonic acid;
fatty acid;
Aromatic carboxylic acid;
(Meth) acrylic acid, (meth) acrylic acid dimer, maleic acid, fumaric acid, vinylbenzoic acid, crotonic acid, itaconic acid, unsaturated carboxylic acids such as citraconic acid;
Unsaturated bond-containing phosphoric acids such as 2-hydroxyethyl methacrylate acid phosphate, 2-acryloyloxyethyl acid phosphate, bis (2-methacryloyloxyethyl) phosphate, bis (2-acryloyloxyethyl) phosphate, etc .;
Can be mentioned.
These compounds may have an organic group such as an alkyl group or an aryl group as a substituent, or may be a derivative such as an esterified product.
　前記酸性基含有化合物のアルカリ金属塩の好ましい具体例としては、スチレンスルホン酸ナトリウム、アルキルフェニルスルホン酸ナトリウムが挙げられる。 Preferred specific examples of the alkali metal salt of the acidic group-containing compound include sodium styrene sulfonate and sodium alkylphenyl sulfonate.
＜酸性基含有化合物のアルカリ金属塩を含む重合体＞
　酸性基含有化合物のアルカリ金属塩を含む重合体は、前記酸性基含有化合物のアルカリ金属塩のうち、不飽和結合を有する化合物の単独重合体、または、前記酸性基含有化合物のアルカリ金属塩のうち不飽和結合を有する化合物と他の共重合可能な化合物との共重合体等が挙げられる。これらは、公知の手法にて重合させて得ることができる。
　また、不飽和結合を有する酸性基含有化合物の単独重合体、または、不飽和結合を有する酸性基含有化合物と他の共重合可能な化合物との共重合体の酸性基をアルカリ金属塩化した（共）重合体や、下記他の共重合可能な化合物の（共）重合体に、従来公知の方法で、前記酸性基を導入し、さらに、導入した酸性基をアルカリ金属塩化した（共）重合体であってもよい。 <A polymer containing an alkali metal salt of an acidic group-containing compound>
The polymer containing the alkali metal salt of the acidic group-containing compound is a homopolymer of a compound having an unsaturated bond among alkali metal salts of the acid group-containing compound, or an alkali metal salt of the acid group-containing compound. Examples thereof include copolymers of a compound having an unsaturated bond and other copolymerizable compounds. These can be obtained by polymerizing by a known method.
In addition, alkali metals of acid group of homopolymer of acid group-containing compound having unsaturated bond, or copolymer of acid group-containing compound having unsaturated bond and other copolymerizable compound are alkali metal chloride (co (Co) polymer obtained by introducing the above-mentioned acidic group into a polymer or a (co) polymer of the following other copolymerizable compound by a conventionally known method, and further introducing the introduced acidic group into an alkali metal It may be
　前記他の共重合可能な化合物としては、例えば、
　メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、３，５，５－トリメチルヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、セチル（メタ）アクリレート、ステアリル（メタ）アクリレート等のアルキル（メタ）アクリレート；
　メトキシメチル（メタ）アクリレート、２－メトキシエチル（メタ）アクリレート、エトキシメチル（メタ）アクリレート、２－エトキシエチル（メタ）アクリレート、４－メトキシブチル（メタ）アクリレート、メトキシプロピル（メタ）アクリレート、エトキシプロピル（メタ）アクリレート、プロポキシエチル（メタ）アクリレート、２－ブトキシエチル（メタ）アクリレート、イソブトキシブチルジグリコール（メタ）アクリレート、フェノキシエチル（メタ）アクリレート等のアルコキシアルキル（メタ）アクリレート；
　ヒドロキシメチル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレート；
　ビニルアルキルエーテル、酢酸ビニル、ビニルアルコール、塩化ビニル、塩化ビニリデン、スチレン、ビニルトルエン、２－ビニルナフタレン、ビニルピリジン等のビニル系化合物；
　エチレン、プロピレン、ブチレン、ブタジエン、ジイソブチレン等のオレフィン系化合物：
　アクリロニトリル、(メタ)アクリルアミド、ジアセトンアクリルアミド等の含窒素化合物；
が挙げられる。 As said other copolymerizable compound, for example,
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, Hexyl (meth) acrylate, heptyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 3,5,5-trimethylhexyl (meth) acrylate Alkyl (meth) acrylates such as lauryl (meth) acrylate, cetyl (meth) acrylate and stearyl (meth) acrylate;
Methoxymethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, methoxypropyl (meth) acrylate, ethoxypropyl (Meth) acrylates, propoxyethyl (meth) acrylates, 2-butoxyethyl (meth) acrylates, isobutoxybutyl diglycol (meth) acrylates, and alkoxyalkyl (meth) acrylates such as phenoxyethyl (meth) acrylates;
Hydroxyalkyl such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate (Meth) acrylates;
Vinyl compounds such as vinyl alkyl ether, vinyl acetate, vinyl alcohol, vinyl chloride, vinylidene chloride, styrene, vinyl toluene, 2-vinyl naphthalene, vinyl pyridine and the like;
Olefin compounds such as ethylene, propylene, butylene, butadiene and diisobutylene:
Nitrogen-containing compounds such as acrylonitrile, (meth) acrylamide, diacetone acrylamide and the like;
Can be mentioned.
　抗ウイルス剤（Ａ）が、酸性基含有化合物のアルカリ金属塩を含む重合体である場合、該重合体の重量平均分子量（Ｍｗ）は、取扱性に優れる組成物が得られ、抗ウイルス性により優れる硬化被膜を容易に得ることができる等の点から、好ましくは５千以上、より好ましくは２万以上、更に好ましくは５万以上、特に好ましくは１０万以上であり、好ましくは５００万以下であり、より好ましくは２００万以下であり、更に好ましくは１００万以下である。 When the antiviral agent (A) is a polymer containing an alkali metal salt of an acidic group-containing compound, the weight average molecular weight (Mw) of the polymer gives a composition excellent in handleability, and the antiviral property From the viewpoint of being able to easily obtain an excellent cured film, etc., it is preferably at least 5,000, more preferably at least 20,000, further preferably at least 50,000, particularly preferably at least 100,000, preferably at least 5,000,000. More preferably, it is 2 million or less, more preferably 1 million or less.
　抗ウイルス剤（Ａ）が、酸性基含有化合物のアルカリ金属塩を含む重合体である場合、酸性基含有化合物のアルカリ金属塩（酸性基含有化合物のアルカリ金属塩構造）の含有量は、抗ウイルス性により優れる硬化被膜を容易に得ることができる等の点から、該重合体全体に対し、２０モル％以上が好ましい。
　特に、前記酸性基がスルホン酸基である場合には、スルホン酸基含有化合物のアルカリ金属塩（スルホン酸基含有化合物のアルカリ金属塩構造）の含有量が前記範囲にあると、硬化被膜が水分に接触した場合でも、該被膜の白化を抑制することができる。 When the antiviral agent (A) is a polymer containing an alkali metal salt of an acidic group-containing compound, the content of the alkali metal salt of the acidic group-containing compound (alkali metal salt structure of the acidic group-containing compound) is 20 mol% or more is preferable with respect to the said whole polymer from the point that the cured film which is excellent by property can be obtained easily.
In particular, when the acid group is a sulfonic acid group, the content of the alkali metal salt of the sulfonic acid group-containing compound (alkali metal salt structure of the sulfonic acid group-containing compound) falls within the above range, the cured film becomes moisture Even in the case of contact with the above, whitening of the film can be suppressed.
　また、抗ウイルス剤（Ａ）が、酸性基含有化合物のアルカリ金属塩を含む重合体である場合、その分子中における酸性基（分子中における酸性基および酸性基の塩の基（塩とされた酸性基）の合計）のうち、塩とされた酸性基の割合は、本組成物の酸性度を適切な範囲に保ち、安定性により優れる組成物を容易に得ることができる等の点から、好ましくは５０モル％以上、より好ましくは７０～１００モル％、特に好ましくは８５～１００モル％である。 When the antiviral agent (A) is a polymer containing an alkali metal salt of an acidic group-containing compound, the acidic group in the molecule (acidic group in the molecule and the salt group of the acidic group (salt) The ratio of the acid group regarded as a salt among the total of the acid groups) maintains the acidity of the present composition in an appropriate range, and from the viewpoint of being able to easily obtain a composition which is more excellent in stability, etc. It is preferably 50 mol% or more, more preferably 70 to 100 mol%, and particularly preferably 85 to 100 mol%.
　酸性基含有化合物のアルカリ金属塩および酸性基含有化合物のアルカリ金属塩を含む重合体は、耐水性に優れる抗ウイルス剤（Ａ）を得ることができる等の点から、さらに架橋剤によって架橋されていてもよい。該架橋剤としては、エポキシ化合物、グリシジル化合物、アジリジン化合物、オキサゾリン化合物、アミン化合物、ポリアミノアミド化合物、イミダゾール化合物、ヒドラジド化合物、メラミン化合物、酸無水物、フェノール化合物、熱潜在性カチオン重合触媒、光潜在性カチオン重合開始剤、ジシアンアミドおよびその誘導体、ジビニルベンゼン等が挙げられる。 The polymer containing the alkali metal salt of the acid group-containing compound and the alkali metal salt of the acid group-containing compound is further crosslinked by a crosslinking agent from the viewpoint that an antiviral agent (A) excellent in water resistance can be obtained. May be Examples of the crosslinking agent include epoxy compounds, glycidyl compounds, aziridine compounds, oxazoline compounds, amine compounds, polyaminoamide compounds, imidazole compounds, hydrazide compounds, melamine compounds, acid anhydrides, phenol compounds, heat latent cationic polymerization catalysts, and photolattices. Cationic polymerization initiators, dicyanamide and its derivatives, divinylbenzene and the like.
　抗ウイルス剤（Ａ）は、タルク、ベントナイト、クレー、カオリン、珪藻土、シリカ、バーミキュライト、パーライト等の無機担体や、ポリエチレン、ポリプロピレン等の有機高分子担体に固定された粒子状の抗ウイルス剤であってもよい。 The antiviral agent (A) is a particulate antiviral agent immobilized on an inorganic carrier such as talc, bentonite, clay, kaolin, diatomaceous earth, silica, vermiculite, perlite, or an organic polymer carrier such as polyethylene or polypropylene. May be
　粒子状の抗ウイルス剤（Ａ）のレーザー回折式粒子径分布測定装置で測定した平均粒子径は、抗ウイルス性により優れる硬化被膜を容易に得ることができる等の点から、好ましくは０．５～３０μｍ、より好ましくは１～２５μｍである。なお、前記平均粒子径は、体積基準の粒度分布における累積５０％の粒径（いわゆるメディアン径Ｄ５０）を指す。
　平均粒子径が前記範囲にある抗ウイルス剤（Ａ）は、硬化被膜から脱落し難いため、抗ウイルス性の持続性により優れる硬化被膜を得ることができる。また、顔料（Ｄ）よりも平均粒子径が大きい抗ウイルス剤（Ａ）を用いると、硬化被膜の表面に抗ウイルス剤（Ａ）が配向し、抗ウイルス性がより優れる硬化被膜を得ることができる。 The average particle diameter of the particulate antiviral agent (A) measured by the laser diffraction particle size distribution measuring device is preferably 0.5, from the viewpoint of easily obtaining a cured film which is more excellent in antiviral property. It is -30 μm, more preferably 1-25 μm. In addition, the said average particle diameter points out the particle size (what is called median diameter D50) of 50% of accumulation in the particle size distribution on a volume basis.
The antiviral agent (A) having an average particle diameter in the above range is unlikely to be detached from the cured film, and therefore, a cured film can be obtained which is more excellent in antiviral persistence. In addition, when an antiviral agent (A) having an average particle diameter larger than that of the pigment (D) is used, the antiviral agent (A) is oriented on the surface of the cured film to obtain a cured film having more excellent antiviral properties. it can.
　抗ウイルス剤（Ａ）は、分散媒によって分散している分散液の形態で用いてもよい。
　前記分散媒としては、特に制限されず、水や有機溶剤等の従来公知の分散媒を用いることができ、該有機溶剤としては、芳香族炭化水素類（例：キシレン、トルエン）、ケトン類（例：メチルイソブチルケトン、メチルエチルケトン、シクロヘキサノン）、エステル類（例：酢酸エチル、酢酸ブチル、酢酸イソブチル）、アルコール類（例：イソプロピルアルコール、ブタノール）、グリコールエーテル類（例：プロピレングリコールモノメチルエーテル）等が挙げられる。 The antiviral agent (A) may be used in the form of a dispersion dispersed by a dispersion medium.
The dispersion medium is not particularly limited, and conventionally known dispersion media such as water and organic solvents can be used, and as the organic solvent, aromatic hydrocarbons (eg, xylene, toluene), ketones (eg, ketones) Examples: methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, esters (eg: ethyl acetate, butyl acetate, isobutyl acetate), alcohols (eg: isopropyl alcohol, butanol), glycol ethers (eg: propylene glycol monomethyl ether), etc. It can be mentioned.
　本組成物の固形分１００質量％に対する抗ウイルス剤（Ａ）の配合量は、抗ウイルス性により優れ、さらに、硬度や耐水性により優れる硬化被膜を得ることができる等の点から、好ましくは０．５～１５質量％、より好ましくは１～１０質量％、特に好ましくは２～５質量％である。
　配合量が前記範囲を下回ると、得られる硬化被膜は十分な抗ウイルス性を発現しないおそれがあり、また、配合量が前記範囲を超えると、硬化被膜の硬度や耐水性が低下するおそれがある。 The compounding quantity of the antiviral agent (A) with respect to solid content of 100% by mass of the present composition is preferably 0 in terms of being able to obtain a cured film which is more excellent in antiviral property and further excellent in hardness and water resistance. The content is preferably 5 to 15% by mass, more preferably 1 to 10% by mass, and particularly preferably 2 to 5% by mass.
If the compounding amount is less than the above range, the resulting cured film may not exhibit sufficient antiviral properties, and if the compounding amount exceeds the above range, the hardness or water resistance of the cured film may be reduced. .
＜光硬化性樹脂（Ｂ）＞
　光硬化性樹脂（Ｂ）は、光硬化性であって、酸性基含有化合物のアルカリ金属塩を含む重合体以外の樹脂であれば特に制限されないが、光硬化性樹脂（Ｂ）としては、例えば、少なくとも１つの不飽和二重結合を有するオリゴマーおよびポリマーが挙げられる。
　本組成物に用いられる樹脂（Ｂ）は、１種でも２種以上でもよい。 <Photocurable resin (B)>
The photocurable resin (B) is not particularly limited as long as it is a photocurable resin other than a polymer containing an alkali metal salt of an acidic group-containing compound, but as the photocurable resin (B), for example, And oligomers and polymers having at least one unsaturated double bond.
The resin (B) used in the present composition may be one kind or two or more kinds.
　前記不飽和二重結合としては、例えば、（メタ）アクリロイル基、ビニル基、アリル基、スチリル基が挙げられ、活性エネルギー線照射時の反応性等の点から、（メタ）アクリロイル基が好ましい。
　樹脂（Ｂ）としては、例えば、ポリエステル（メタ）アクリレート系樹脂、エポキシ（メタ）アクリレート系樹脂、ポリエーテル（メタ）アクリレート系樹脂およびウレタン（メタ）アクリレート系樹脂が挙げられる。 Examples of the unsaturated double bond include a (meth) acryloyl group, a vinyl group, an allyl group and a styryl group, and a (meth) acryloyl group is preferable from the viewpoint of reactivity at the time of active energy ray irradiation.
Examples of the resin (B) include polyester (meth) acrylate resins, epoxy (meth) acrylate resins, polyether (meth) acrylate resins and urethane (meth) acrylate resins.
　ポリエステル（メタ）アクリレート系樹脂としては、例えば、多塩基酸またはその無水物と多価アルコールとから合成されるポリエステルに、（メタ）アクリル酸を反応させて得られるポリエステル（メタ）アクリレート系樹脂が挙げられる。
　前記多塩基酸としては、例えば、フタル酸、コハク酸、アジピン酸、グルタル酸、セバシン酸、イソセバシン酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ダイマー酸、トリメリット酸、ピロメリット酸、ピメリン酸、アゼライン酸が挙げられる。
　前記多価アルコールとしては、例えば、１，６－ヘキサンジオール、ジエチレングリコール、１，２－プロピレングリコール、１，３－ブチレングリコール、ネオペンチルグリコール、ジプロピレングリコール、ポリエチレングリコール、ポリプロピレングリコールが挙げられる。 As polyester (meth) acrylate resin, for example, polyester (meth) acrylate resin obtained by reacting (meth) acrylic acid with polyester synthesized from polybasic acid or its anhydride and polyhydric alcohol It can be mentioned.
Examples of the polybasic acids include phthalic acid, succinic acid, adipic acid, glutaric acid, sebacic acid, isoecebacic acid, tetrahydrophthalic acid, hexahydrophthalic acid, dimer acid, trimellitic acid, pyromellitic acid, pimelic acid, And azelaic acid.
Examples of the polyhydric alcohol include 1,6-hexanediol, diethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, neopentyl glycol, dipropylene glycol, polyethylene glycol and polypropylene glycol.
　エポキシ（メタ）アクリレート系樹脂としては、例えば、エポキシ樹脂に、（メタ）アクリル酸を付加させて得られる（メタ）アクリル酸変性エポキシ系樹脂が挙げられる。
　変性に供される前記エポキシ樹脂としては、例えば、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳまたはフェノールノボラックと、エピクロルヒドリンとを反応させて得られる樹脂、シクロペンタジエンオキシドまたはシクロヘキセンオキシドと、エピクロルヒドリンとを反応させて得られる樹脂が挙げられる。 Examples of epoxy (meth) acrylate resins include (meth) acrylic acid-modified epoxy resins obtained by adding (meth) acrylic acid to epoxy resins.
As the epoxy resin to be subjected to modification, for example, a resin obtained by reacting bisphenol A, bisphenol F, bisphenol S or phenol novolac with epichlorohydrin, cyclopentadiene oxide or cyclohexene oxide and epichlorohydrin are reacted with each other. The obtained resin is mentioned.
　ポリエーテル（メタ）アクリレート系樹脂としては、例えば、ポリエーテルとエチル（メタ）アクリレートなどの（メタ）アクリル酸エステルとのエステル交換反応によって得られるポリエーテル（メタ）アクリレート系樹脂が挙げられる。
　前記ポリエーテルとしては、例えば、トリメチロールプロパンおよびペンタエリスリトールなどをエトキシ化やプロポキシ化などすることにより得られたポリエーテル、１，４－ブタンジオールなどをポリエーテル化することにより得られたポリエーテルが挙げられる。 Examples of polyether (meth) acrylate resins include polyether (meth) acrylate resins obtained by transesterification of polyether and (meth) acrylic acid ester such as ethyl (meth) acrylate.
Examples of the polyether include polyethers obtained by ethoxylation or propoxylation of trimethylolpropane and pentaerythritol and the like, and polyethers obtained by polyetherifying 1,4-butanediol and the like. Can be mentioned.
　ウレタン（メタ）アクリレート系樹脂としては、例えば、イソシアネート化合物と、ヒドロキシ基含有（メタ）アクリレート化合物と、任意にポリオール化合物とを反応させて得られるウレタン（メタ）アクリレート系樹脂が挙げられる。
　前記イソシアネート化合物としては、例えば、トリレンジイソシアネート、キシリレンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネートが挙げられる。
　前記ヒドロキシ基含有（メタ）アクリレート化合物としては、例えば、ヒドロキシメチル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレートなどの（メタ）アクリル酸の水酸基含有アルキルエステルが挙げられる。
　前記ポリオール化合物としては、例えば、水素化ビスフェノールＡとエチレンオキサイドとの付加物、水素化ビスフェノールＡ、ネオペンチルグリコール、１，６－ヘキサンジオール、トリメチロールプロパンが挙げられる。 Examples of urethane (meth) acrylate resins include urethane (meth) acrylate resins obtained by reacting an isocyanate compound, a hydroxy group-containing (meth) acrylate compound, and optionally a polyol compound.
Examples of the isocyanate compound include tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate.
Examples of the hydroxy group-containing (meth) acrylate compound include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4- Examples thereof include hydroxyl group-containing alkyl esters of (meth) acrylic acid such as hydroxybutyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate.
Examples of the polyol compound include an adduct of hydrogenated bisphenol A and ethylene oxide, hydrogenated bisphenol A, neopentyl glycol, 1,6-hexanediol, and trimethylolpropane.
　本組成物の固形分１００質量％に対する樹脂（Ｂ）の配合量は、硬度および耐傷性に優れる硬化被膜を容易に得ることができ、硬化被膜を形成する際の硬化収縮を抑制できる等の点から、好ましくは３～３０質量％、より好ましくは５～２５質量％、特に好ましくは１０～２０質量％である。
　配合量が前記範囲を下回ると、得られる硬化被膜の硬度や耐傷性が低下するおそれがあり、また、配合量が前記範囲を超えると、硬化被膜を形成する際の硬化収縮が大きくなりすぎるおそれがある。 The compounding amount of the resin (B) relative to 100% by mass of the solid content of the present composition can easily obtain a cured film excellent in hardness and scratch resistance, and can suppress curing shrinkage when forming the cured film, etc. It is preferably 3 to 30% by mass, more preferably 5 to 25% by mass, and particularly preferably 10 to 20% by mass.
If the amount is less than the above range, the hardness and the scratch resistance of the resulting cured film may be reduced. If the amount is more than the range, the cure shrinkage upon forming the cured film may be too large. There is.
＜不飽和単量体（Ｃ）＞
　不飽和単量体（Ｃ）としては、不飽和二重結合を１つ有する単官能モノマー、不飽和二重結合を２つ有する２官能モノマー、不飽和二重結合を３つ以上有する３官能以上の多官能モノマーが挙げられる。これらのモノマーの中でも、より光硬化性に優れ、抗ウイルス性に優れる硬化被膜を容易に得ることができる等の点から、（メタ）アクリレート系モノマーが好ましい。
　本組成物に用いられる不飽和単量体（Ｃ）は、１種でも２種以上でもよく、単官能モノマーおよび２官能モノマーの少なくとも１つを用いることが、粘度が低く、塗装作業性により優れる本組成物を容易に得ることができる等の点から好ましい。 <Unsaturated Monomer (C)>
As unsaturated monomer (C), monofunctional monomer having one unsaturated double bond, bifunctional monomer having two unsaturated double bonds, trifunctional or more having three or more unsaturated double bonds And polyfunctional monomers. Among these monomers, (meth) acrylate monomers are preferable from the viewpoint of being able to easily obtain a cured film which is more excellent in photocurability and excellent in antiviral property.
The unsaturated monomer (C) used in the present composition may be of one type or two or more types, and using at least one of a monofunctional monomer and a bifunctional monomer is low in viscosity and excellent in coating workability. It is preferable from the point that this composition can be obtained easily.
　単官能モノマーとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、イソアミル（メタ）アクリレート、ヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、３，５，５－トリメチルヘキシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、トリデシル（メタ）アクリレート、イソミリスチル（メタ）アクリレート、アルキル（メタ）アクリレート（Ｃ１２～Ｃ１３）、セチル（メタ）アクリレート、２－メトキシエチル（メタ）アクリレート、３－メトキシブチル（メタ）アクリレート、ステアリル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、エトキシ－ジエチレングリコール（メタ）アクリレート、メトキシ－トリエチレングリコール（メタ）アクリレート、メトキシ－ポリエチレングリコール（メタ）アクリレート（ｎ≒９）、メトキシジプロピレングリコール（メタ）アクリレート、メトキシトリプロピレングリコール（メタ）アクリレート、ジプロピレングリコール（メタ）アクリレート、２－エチルヘキシル－ジグリコール（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシ－ポリエチレングリコール（メタ）アクリレート、パラクミルフェノールＥＯ変性（メタ）アクリレート、ノニルフェノールＥＯ付加物（メタ）アクリレート（ｎ≒１）、ノニルフェノールＥＯ付加物（メタ）アクリレート（ｎ≒２）、ノニルフェノールＥＯ付加物（メタ）アクリレート（ｎ≒４）、ノニルフェノールＥＯ付加物（メタ）アクリレート（ｎ≒８）、ノニルフェノールＥＯ付加物（メタ）アクリレート（ｎ≒１６～１７）、ノニルフェノールＰＯ変性（メタ）アクリレート（ｎ≒２．５）、テトラヒドロフルフリル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ヒドロキシメチル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート、２－（メタ）アクリロイルオキシエチル－コハク酸、２－（メタ）アクリロイルオキシエチル－フタル酸、２－（メタ）アクリロイルオキシプロピルハイドロゲンフタレート、２－（メタ）アクリロイルオキシプロピルヘキサヒドロハイドロゲンテレフタレート、２－（メタ）アクリロイルオキシプロピルテトラヒドロハイドロゲンテレフタレート、２－（メタ）アクリロイルオキシエチル－ヘキサヒドロフタル酸、２－（メタ）アクリロイルオキシエチル－２－ヒドロキシエチル－フタル酸、２－（メタ）アクリロイルオキシエチル－２－ヒドロキシプロピルフタレート、２－（メタ）アクリロイルオキシエチルアシッドフォスフェート、ジメチルアミノエチル（メタ）アクリレート、ジメチルアミノプロピル（メタ）アクリルアミド、トリフルオロエチル（メタ）アクリレート、テトラフルオロプロピル（メタ）アクリレート、オクタフルオロペンチル（メタ）アクリレート、パーフルオロオクチルエチル（メタ）アクリレート、ω－カルボキシ－カプロラクトン（ｎ≒２）モノ（メタ）アクリレート、アクリル酸ダイマー（ｎ≒１．４）、Ｎ－ビニル－２－ピロリドン、アクリロニトリル、（メタ）アクリルアミド、ジアセトンアクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチル（メタ）アクリルアミド、（メタ）アクリロイルモルフォリン、Ｎ－イソプロピル（メタ）アクリルアミド、Ｎ－２－ヒドロキシエチル（メタ）アクリルアミド、カプロラクトン（メタ）アクリレート、ネオペンチルグリコール（メタ）アクリル酸安息香酸エステル、トリブロモフェニル（メタ）アクリレート、ＥＯ変性トリブロモフェニル（メタ）アクリレート、ビニルアルキルエーテル、酢酸ビニル、ビニルアルコール、塩化ビニル、塩化ビニリデン、スチレン、ビニルトルエン、２－ビニルナフタレン、ビニルピリジン、エチレン、プロピレン、ブチレン、ジイソブチレンが挙げられる。
　なお、本発明において、ＥＯはエチレンオキサイド、ＰＯはプロピレンオキサイドの略であり、ｎはアルキレンオキサイドないしカプロラクトンの繰り返し数で平均値を示す。 Examples of monofunctional monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) Acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 3,5,5-trimethylhexyl (meth) ) Acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, isomyristyl (meth) acrylate, alkyl (meth) acrylate ( 12 to C13), cetyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, stearyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxy-diethylene glycol (meth) acrylate, Methoxy-triethylene glycol (meth) acrylate, methoxy-polyethylene glycol (meth) acrylate (n ≒ 9), methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, dipropylene glycol (meth) acrylate, 2-Ethylhexyl-diglycol (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate , Phenoxy-polyethylene glycol (meth) acrylate, paracumylphenol EO modified (meth) acrylate, nonylphenol EO adduct (meth) acrylate (n ≒ 1), nonylphenol EO adduct (meth) acrylate (n ≒ 2), nonylphenol EO adduct (meth) acrylate (n ≒ 4), nonylphenol EO adduct (meth) acrylate (n ≒ 8), nonylphenol EO adduct (meth) acrylate (n ≒ 16 to 17), nonylphenol PO modified (meth) acrylate (N ≒ 2.5), tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrelay 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-succinic acid, 2- (meth) Acryloyloxyethyl-phthalic acid, 2- (meth) acryloyloxypropyl hydrogen phthalate, 2- (meth) acryloyloxypropyl hexahydrohydrogen terephthalate, 2- (meth) acryloyloxypropyltetrahydrohydrogen terephthalate, 2- (meth) acryloyloxy Ethyl-hexahydrophthalic acid, 2- (meth) acryloyloxyethyl-2-hydroxyethyl-phthalic acid, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 2 (Meth) acryloyloxyethyl acid phosphate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, Perfluorooctylethyl (meth) acrylate, ω-carboxy-caprolactone (n ≒ 2) mono (meth) acrylate, acrylic acid dimer (n ≒ 1.4), N-vinyl-2-pyrrolidone, acrylonitrile, (meth) acrylamide Diacetone acrylamide, N, N-dimethyl (meth) acrylamide, N, N- diethyl (meth) acrylamide, (meth) acryloyl morpholine, N- isopropyl (meth) acrylamide N, N-2-hydroxyethyl (meth) acrylamide, caprolactone (meth) acrylate, neopentyl glycol (meth) acrylic acid benzoate, tribromophenyl (meth) acrylate, EO modified tribromophenyl (meth) acrylate, vinyl Alkyl ethers, vinyl acetate, vinyl alcohol, vinyl chloride, vinylidene chloride, styrene, vinyl toluene, 2-vinyl naphthalene, vinyl pyridine, ethylene, propylene, butylene and diisobutylene can be mentioned.
In the present invention, EO is an abbreviation for ethylene oxide, and PO is an abbreviation for propylene oxide, and n is an average value of the repeating numbers of alkylene oxide to caprolactone.
　２官能モノマーとしては、例えば、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、ＰＥＧ２００＃ジ（メタ）アクリレート（ＥＯ部がｎ≒４）、テトラエチレングリコールジ（メタ）アクリレート、ＰＥＧ３００＃ジ（メタ）アクリレート（ＥＯ部がｎ≒６）、ＰＥＧ４００＃ジ（メタ）アクリレート（ＥＯ部がｎ≒９）、ＰＥＧ６００＃ジ（メタ）アクリレート（ＥＯ部がｎ≒１３～１４）、ポリエチレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ＰＯ付加ネオペンチルグリコールジ（メタ）アクリレート、３－メチル－１，５－ペンタンジオールジ（メタ）アクリレート、ヒドロキシピバリン酸ネオペンチルグリコールジ（メタ）アクリレート、ポリテトラメチレングリコールジ（メタ）アクリレート、１，３－ブタンジオールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、２－ブチル－２－エチル－１，３－プロパンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、ＥＯ変性トリメチロールプロパンジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ジメチロール－トリシクロデカンジ（メタ）アクリレート、ビスフェノールＦのＥＯ変性ジ（メタ）アクリレート、ビスフェノールＡのＥＯ付加物ジ（メタ）アクリレート、水添加ビスフェノールＡのＥＯ付加物ジ（メタ）アクリレート、ビスフェノールＡのＰＯ付加物ジ（メタ）アクリレート、ペンタエリストールジ（メタ）アクリレートモノステアレート、イソシアヌル酸ＥＯ変性ジ（メタ）アクリレート、２－ヒドロキシ－３－（メタ）アクリロイルオキシプロピル（メタ）アクリレート、ジンクジ（メタ）アクリレート、ブタジエンが挙げられる。 As a bifunctional monomer, for example, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, PEG200 # di (meth) acrylate (EO part is n ≒ 4), tetraethylene glycol di (meth) acrylate, PEG300 # Di (meth) acrylate (EO part n 6 6), PEG 400 # di (meth) acrylate (EO part n 9 9), PEG 600 # di (meth) acrylate (EO part n 13 14), polyethylene Glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, PO-added neopentyl glycol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) Acrylate, hydroxide Pivalate neopentyl glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexane Diol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, EO modified trimethylolpropane di (meth) acrylate, Polypropylene glycol di (meth) acrylate, dimethylol-tricyclodecane di (meth) acrylate, EO modified di (meth) acrylate of bisphenol F, EO adduct of bisphenol A di (meth) acrylate, EO adduct of water-added bisphenol A The ) Acrylate, PO adduct of bisphenol A di (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, isocyanurate EO modified di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl ( Examples include meta) acrylates, zinc di (meth) acrylates and butadiene.
　また、３官能以上の多官能モノマーとしては、例えば、トリメチロールプロパントリ（メタ）アクリレート、ＥＯ変性トリメチロールプロパントリ（メタ）アクリレート、ＰＯ変性トリメチロールプロパントリ（メタ）アクリレート（ＰＯ＝２）、ＰＯ変性トリメチロールプロパントリ（メタ）アクリレート（ＰＯ＝３）、トリメチロールプロパントリ（メタ）アクリル酸安息香酸エステル、グリセリンＰＯ付加トリ（メタ）アクリレート、ＰＯ付加グリコールトリ（メタ）アクリレート、トリス（メタ）アクリロイルオキシエチルフォスフェート、ペンタエリスリトールトリ（メタ）アクリレート、ＥＯ付加ペンタエリスリトールトリ（メタ）アクリレート、トリス［（メタ）アクリロイルオキシエチル］イソシアヌレート、ペンタエリスリトールテトラ（メタ）アクリレート、ＥＯ付加ペンタエリスリトールテトラ（メタ）アクリレート、ジメチロールプロパンテトラ（メタ）アクリレート、ジペンタエリスリトールヒドロキシペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレートが挙げられる。 Moreover, as a trifunctional or higher polyfunctional monomer, for example, trimethylolpropane tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, PO modified trimethylolpropane tri (meth) acrylate (PO = 2), PO modified trimethylolpropane tri (meth) acrylate (PO = 3), trimethylolpropane tri (meth) acrylic acid benzoate, glycerin PO addition tri (meth) acrylate, PO addition glycol tri (meth) acrylate, tris (meth) ) Acryloyloxyethyl phosphate, pentaerythritol tri (meth) acrylate, EO-added pentaerythritol tri (meth) acrylate, tris [(meth) acryloyloxyethyl] isocyanurate, pentaeriol Ritorutetora (meth) acrylate, EO-added pentaerythritol tetra (meth) acrylate, dimethylol propane tetra (meth) acrylate, dipentaerythritol hydroxy penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate.
　本組成物の固形分１００質量％に対する不飽和単量体（Ｃ）の配合量は、塗工性に優れる組成物を容易に得ることができ、硬化被膜を形成する際の硬化不良を抑制でき、所望の硬度を有する硬化被膜を容易に得ることができる等の点から、好ましくは４０～９０質量％、より好ましくは４５～８５質量％、特に好ましくは５０～８０質量％である。
　配合量が前記範囲を下回ると、得られる組成物の粘度が高くなり塗工性が低下するおそれがあり、また、配合量が前記範囲を超えると、硬化被膜の硬度低下や硬化被膜を形成する際の硬化不良が起こるおそれがある。 The compounding quantity of the unsaturated monomer (C) with respect to solid content 100 mass% of this composition can obtain easily the composition which is excellent in coating property, and can suppress the curing defect at the time of forming a cured film. The amount is preferably 40 to 90% by mass, more preferably 45 to 85% by mass, and particularly preferably 50 to 80% by mass from the viewpoint that a cured film having a desired hardness can be easily obtained.
If the compounding amount is less than the above range, the viscosity of the composition obtained may be increased and the coatability may be reduced, and if the compounding amount exceeds the above range, the hardness of the cured film is reduced or a cured film is formed. Poor curing may occur.
　なお、光硬化性樹脂（Ｂ）と不飽和単量体（Ｃ）の配合比率は、成分（Ｂ）および成分（Ｃ）の合計１００質量％に対して、成分（Ｂ）が２０質量％以下であることが、抗ウイルス性により優れる硬化被膜が得られる等の点から好ましい。 The blending ratio of the photocurable resin (B) to the unsaturated monomer (C) is 20% by mass or less of the component (B) based on 100% by mass in total of the component (B) and the component (C) It is preferable from the point that the cured film which is more excellent in antiviral property is obtained.
＜顔料（Ｄ）＞
　顔料（Ｄ）としては、従来公知の顔料を用いることができる。なお、顔料（Ｄ）は、前記成分（Ａ）～（Ｃ）および（Ｅ）以外の粒子である。
　本組成物は、顔料（Ｄ）を用いるため、表面に凹凸を有する硬化被膜を得ることができ、抗ウイルス剤（Ａ）とウイルスとが接する面積が増大すると考えられる。更に、抗ウイルス剤（Ａ）の分散性を向上させ、硬化被膜表面へ均一に配向させることができると考えられる。このため、抗ウイルス性に優れる硬化被膜を容易に得ることができる。
　本組成物に用いられる顔料（Ｄ）は、１種でも２種以上でもよい。 <Pigment (D)>
As the pigment (D), conventionally known pigments can be used. The pigment (D) is particles other than the components (A) to (C) and (E).
Since this composition uses a pigment (D), a cured film having irregularities on the surface can be obtained, and it is considered that the area in which the antiviral agent (A) and the virus are in contact is increased. Furthermore, it is considered that the dispersibility of the antiviral agent (A) can be improved and it can be uniformly oriented on the surface of the cured film. For this reason, the cured film which is excellent in antiviral property can be obtained easily.
The pigment (D) used in the present composition may be one kind or two or more kinds.
　顔料（Ｄ）としては、アクリル微粒子、ポリスチレン微粒子、ポリエチレンワックス微粒子、ポリプロピレンワックス微粒子、ＰＴＦＥ微粒子、ウレタン微粒子、シリコーン微粒子などの有機樹脂微粒子（有機樹脂ビーズ）、金属酸化物微粒子（例：シリカ微粒子、酸化アルミニウム微粒子、酸化ジルコニウム微粒子、酸化亜鉛微粒子、酸化チタン微粒子）などの無機微粒子が挙げられる。
　これらの中でも、抗ウイルス性により優れる硬化被膜を容易に得ることができ、抗ウイルス剤（Ａ）の分散性に優れる組成物を容易に得ることができる等の点から、無機微粒子が好ましく、シリカ微粒子がより好ましい。 As the pigment (D), organic resin particles (organic resin beads) such as acrylic particles, polystyrene particles, polyethylene wax particles, polypropylene wax particles, PTFE particles, urethane particles, silicone particles, metal oxide particles (eg, silica particles, Inorganic fine particles such as aluminum oxide fine particles, zirconium oxide fine particles, zinc oxide fine particles, titanium oxide fine particles) can be mentioned.
Among these, from the viewpoint that a cured film which is more excellent in antiviral property can be easily obtained and a composition which is excellent in dispersibility of the antiviral agent (A) can be easily obtained, inorganic fine particles are preferable, silica Microparticles are more preferred.
　顔料（Ｄ）の平均粒子径は、特に限定されないが、好ましくは１～１０μｍ、より好ましくは２～８μｍである。
　平均粒子径が前記範囲の下限以上の顔料（Ｄ）を用いることにより、得られる硬化被膜の表面に適度な粗さの凹凸を形成することができ、塗膜表面の抗ウイルス剤（Ａ）とウイルスとの接触面積が大きくなることから、抗ウイルス性により優れる硬化被膜を容易に得ることができる。また、平均粒子径が前記範囲の上限以下の顔料（Ｄ）を用いることにより、得られる硬化被膜から顔料（Ｄ）の脱落を抑制でき、得られる硬化被膜の抗ウイルス性を長期に亘り維持できる。
　なお、前記平均粒子径は、体積基準の粒度分布における累積５０％の粒径（いわゆるメディアン径Ｄ５０）のことをいい、レーザー回折式粒子径分布測定装置で測定できる。 The average particle size of the pigment (D) is not particularly limited, but preferably 1 to 10 μm, more preferably 2 to 8 μm.
By using the pigment (D) having an average particle diameter equal to or more than the lower limit of the above range, it is possible to form irregularities of appropriate roughness on the surface of the cured film to be obtained. Since the contact area with the virus is increased, a cured film which is more excellent in antiviral property can be easily obtained. In addition, by using the pigment (D) having an average particle diameter equal to or less than the upper limit of the above range, detachment of the pigment (D) can be suppressed from the obtained cured film, and the antiviral property of the obtained cured film can be maintained for a long time .
The average particle diameter refers to the cumulative 50% particle diameter (so-called median diameter D50) in the volume-based particle size distribution, and can be measured by a laser diffraction particle size distribution measuring device.
　顔料（Ｄ）の顔料容積濃度（以下「ＰＶＣ」ともいう。）の下限は、好ましくは２％、より好ましくは３％、特に好ましくは５％である。上限は、好ましくは２５％、より好ましくは２０％、特に好ましくは１５％である。
　前記ＰＶＣが前記範囲の下限以上であると、得られる硬化被膜の表面に適度な粗さの凹凸を形成することができ、塗膜表面の抗ウイルス剤（Ａ）とウイルスとの接触面積が大きくなることから、抗ウイルス性により優れる硬化被膜を容易に得ることができる。また、前記ＰＶＣが前記範囲の上限を超えると、得られる硬化被膜中の顔料の割合が高くなることから、硬化被膜が脆くなるおそれがある。 The lower limit of the pigment volume concentration (hereinafter also referred to as "PVC") of the pigment (D) is preferably 2%, more preferably 3%, particularly preferably 5%. The upper limit is preferably 25%, more preferably 20%, particularly preferably 15%.
When the PVC is at least the lower limit of the above range, irregularities of appropriate roughness can be formed on the surface of the resulting cured film, and the contact area between the antiviral agent (A) on the surface of the coating film and the virus is large. Thus, a cured film which is more excellent in antiviral property can be easily obtained. Moreover, when the said PVC exceeds the upper limit of the said range, since the ratio of the pigment in the cured film obtained will become high, there exists a possibility that a cured film may become brittle.
　前記ＰＶＣは、本組成物中の固形分の容積に対する、顔料（Ｄ）の合計の容積濃度のことをいう。具体的には下記式より求めることができる。
　ＰＶＣ＝顔料（Ｄ）の容積×１００／本組成物中の固形分の容積
　なお、本実施形態において、固形分とは、本組成物から有機溶剤などの揮発成分を除いた成分であり、硬化させたときに硬化被膜として残存する成分を示す。
　前記本組成物中の固形分の容積は、本組成物の固形分の質量および真密度から算出することができる。前記固形分の質量および真密度は、測定値でも、用いる原料から算出した値でも構わない。
　前記顔料（Ｄ）の容積は、用いた顔料（Ｄ）の質量および真密度から算出することができる。前記顔料（Ｄ）の質量および真密度は、測定値でも、用いる原料から算出した値でも構わない。例えば、本組成物の固形分より顔料（Ｄ）と他の成分とを分離し、分離された顔料（Ｄ）の質量および真密度を測定することで算出することができる。 Said PVC refers to the total volume concentration of the pigment (D) with respect to the volume of solids in the present composition. Specifically, it can be obtained from the following equation.
PVC = volume of pigment (D) × 100 / volume of solid content in the composition In the present embodiment, the solid content is a component obtained by removing volatile components such as an organic solvent from the composition, and curing The component which remains as a cured film is shown.
The volume of solid content in the present composition can be calculated from the mass and the true density of the solid content of the composition. The mass and the true density of the solid content may be measured values or values calculated from raw materials used.
The volume of the pigment (D) can be calculated from the mass and the true density of the pigment (D) used. The mass and the true density of the pigment (D) may be measured values or values calculated from the raw materials used. For example, it can be calculated by separating the pigment (D) and the other components from the solid content of the present composition, and measuring the mass and true density of the separated pigment (D).
＜光重合開始剤（Ｅ）＞
　光重合開始剤（Ｅ）は、光照射によりラジカルまたはカチオンを発生し、前述の成分（Ｂ）および（Ｃ）を反応させることで本組成物を硬化可能な化合物であれば特に制限されない。
　本組成物に用いられる開始剤（Ｅ）は、１種でも２種以上でもよい。 <Photoinitiator (E)>
The photopolymerization initiator (E) is not particularly limited as long as it is a compound that can generate a radical or a cation upon irradiation with light and react the above components (B) and (C) to cure the present composition.
The initiator (E) used in the present composition may be one kind or two or more kinds.
　開始剤（Ｅ）としては、例えば、アルキルフェノン系開始剤、アシルフォスフィンオキサイド系開始剤、水素引抜型開始剤が挙げられる。 As an initiator (E), an alkyl phenone type initiator, an acyl phosphine oxide type initiator, and a hydrogen abstraction type initiator are mentioned, for example.
　アルキルフェノン系開始剤としては、例えば、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、１－ヒドロキシ－シクロヘキシル－フェニル－ケトン、２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン、１－［４－（２－ヒドロキシエトキシ）－フェニル］－２－ヒドロキシ－２－メチル－１－プロパン－１－オン、２－ヒロドキシ－１－｛４－［４－（２－ヒドロキシ－２－メチル－プロピオニル）－ベンジル］フェニル｝－２－メチル－プロパン－１－オン、２－メチル－１－（４－メチルチオフェニル）－２－モルフォリノプロパン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン－１、２－（ジメチルアミノ）－２－［（４－メチルフェニル）メチル］－１－［４－（４－モルホリニル）フェニル］－１－ブタノンが挙げられる。 As an alkyl phenone type initiator, for example, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane -1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2 -Hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl 1- [4- (4-morpholinyl) phenyl] -1-butanone.
　アシルフォスフィンオキサイド系開始剤としては、例えば、２，４，６－トリメチルベンゾイル－ジフェニル－フォスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイドが挙げられる。 Examples of the acylphosphine oxide initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.
　水素引抜型開始剤としては、例えば、ベンゾフェノン、２，４，６－トリメチルベンゾフェノン、ベンゾイル安息香酸メチル、２，４－ジエチルチオキサントン、２－エチルアントラキノン、カンファーキノン、オキシ－フェニル－アセチックアシッド２－[２－オキソ－２－フェニル－アセトキシ－エトキシ]－エチルエステルとオキシ－フェニル－アセチックアシッド２－[２－ヒドロキシ－エトキシ]－エチルエステルとの混合物、フェニルグリオキシリックアシッドメチルエステルが挙げられる。 Examples of hydrogen abstraction initiators include benzophenone, 2,4,6-trimethylbenzophenone, methyl benzoylbenzoate, 2,4-diethylthioxanthone, 2-ethylanthraquinone, camphorquinone, oxy-phenyl-acetic acid 2- Mixtures of [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester and oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester, including phenylglyoxylic acid methyl ester .
　これらの中でも、１－ヒドロキシ－シクロヘキシル－フェニル－ケトン、２，４，６－トリメチルベンゾイル－ジフェニル－フォスフィンオキサイドが好ましい。 Among these, 1-hydroxy-cyclohexyl-phenyl-ketone and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide are preferable.
　本組成物の固形分１００質量％に対する開始剤（Ｅ）の配合量は、硬化性、硬度および基材との密着性により優れる硬化被膜を容易に得ることができ、さらに、紫外線等による黄変を抑制できる硬化被膜を容易に得ることができる等の点から、好ましくは０．１～１０質量％、より好ましくは３～９質量％、特に好ましくは４～８質量％である。
　配合量が前記範囲を下回ると、硬化被膜を形成する際の硬化性が不十分となり、得られる硬化被膜の硬度が低下するおそれがある。一方、配合量が前記範囲を超えると、未反応の開始剤（Ｅ）が硬化被膜中に残存しやすく、得られる硬化被膜の硬度が低下しやすくなり、硬化被膜が紫外線等により黄変しやすくなり、また、基材との密着性が低下するおそれがある。 The content of the initiator (E) based on 100% by mass of the solid content of the present composition can easily obtain a cured film which is excellent in curability, hardness and adhesion with a substrate, and further yellowing due to ultraviolet light etc. Preferably, the content is 0.1 to 10% by mass, more preferably 3 to 9% by mass, and particularly preferably 4 to 8% by mass, from the viewpoint of easily obtaining a cured film capable of suppressing the above.
If the compounding amount is less than the above range, the curability at the time of forming a cured film may be insufficient, and the hardness of the obtained cured film may be reduced. On the other hand, when the compounding amount exceeds the above range, the unreacted initiator (E) tends to remain in the cured film, the hardness of the obtained cured film tends to decrease, and the cured film is easily yellowed by ultraviolet light and the like. In addition, the adhesion to the substrate may be reduced.
＜その他の添加剤＞
　本組成物には、必要に応じて、前述した成分以外のその他の添加剤を配合してもよい。
　その他の添加剤としては、本発明の分野で通常用いられてきた添加剤を本発明の効果を損なわない範囲で用いることができ、例えば、有機溶剤、レベリング剤、消泡剤、重合禁止剤、非反応性希釈剤、艶消し剤、沈降防止剤、分散剤、熱安定剤、紫外線吸収剤が挙げられる。
　これらの配合量は、本発明の効果を損なわない範囲で適宜調整することができる。
　前記その他の添加剤は、それぞれ、１種を用いてもよく、２種以上を用いてもよい。 <Other additives>
If necessary, other additives other than the components described above may be added to the composition.
As other additives, additives generally used in the field of the present invention can be used in the range not to impair the effects of the present invention, for example, organic solvents, leveling agents, antifoaming agents, polymerization inhibitors, Non-reactive diluents, matting agents, anti-settling agents, dispersing agents, heat stabilizers, UV absorbers may be mentioned.
These compounding quantities can be suitably adjusted in the range which does not impair the effect of this invention.
The other additives may be used alone or in combination of two or more.
＜有機溶剤＞
　本組成物には、粘度を所定の範囲に調整する等の点から、有機溶剤を配合してもよい。
　有機溶剤としては、従来公知の溶剤を用いることができる。例えば、芳香族炭化水素類（例：キシレン、トルエン）、ケトン類（例：メチルイソブチルケトン、メチルエチルケトン、シクロヘキサノン）、エステル類（例：酢酸エチル、酢酸ブチル、酢酸イソブチル）、アルコール類（例：イソプロピルアルコール、ブタノール）、グリコールエーテル類（例：プロピレングリコールモノメチルエーテル）が挙げられる。 <Organic solvent>
The composition may contain an organic solvent from the viewpoint of adjusting the viscosity to a predetermined range.
As the organic solvent, conventionally known solvents can be used. For example, aromatic hydrocarbons (eg: xylene, toluene), ketones (eg: methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone), esters (eg: ethyl acetate, butyl acetate, isobutyl acetate), alcohols (eg: isopropyl Alcohol, butanol), glycol ethers (eg, propylene glycol monomethyl ether) can be mentioned.
＜レベリング剤＞
　本組成物には、該組成物のハジキを改善して、基材面への濡れ性を向上させ、膜厚の均一な硬化被膜を容易に形成できる等の点から、レベリング剤を配合することが好ましい。
　レベリング剤としては、例えば、フッ素系、アクリル系、シリコン系等の各種レベリング剤が挙げられる。
　本組成物の固形分１００質量％に対するレベリング剤の配合量は、好ましくは０．１～１．５質量％、より好ましくは０．２～１．０質量％である。 <Leveling agent>
In the present composition, a leveling agent is blended from the viewpoint of improving the repelling of the composition, improving the wettability to the substrate surface, and easily forming a cured film having a uniform film thickness. Is preferred.
As a leveling agent, various leveling agents, such as fluorine type, an acryl type, and silicon type, are mentioned, for example.
The compounding amount of the leveling agent with respect to 100% by mass of the solid content of the present composition is preferably 0.1 to 1.5% by mass, more preferably 0.2 to 1.0% by mass.
＜消泡剤＞
　本組成物には、該組成物における気泡の発生を抑制し、外観が良好な硬化被膜を容易に形成できる等の点から、消泡剤を配合することが好ましい。
　消泡剤としては、例えば、アクリル系、シリコン系等の各種消泡剤が挙げられる。
　本組成物の固形分１００質量％に対する消泡剤の配合量は、好ましくは０．０００１～１．０質量％である。 <Antifoam>
It is preferable to add an antifoaming agent to the present composition from the viewpoint of suppressing the generation of air bubbles in the composition and easily forming a cured film having a good appearance.
As an antifoamer, various antifoamers, such as an acryl type and a silicon type, are mentioned, for example.
The compounding amount of the antifoaming agent with respect to 100% by mass of the solid content of the present composition is preferably 0.0001 to 1.0% by mass.
＜分散剤＞
　本組成物には、該組成物における顔料（Ｄ）の分散性を向上し、外観が良好な硬化被膜を容易に形成できる等の点から、分散剤を配合してもよい。
　分散剤としては、特に限定されないが、例えば、カルボン酸、リン酸、アミン等の顔料吸着基を有し、脂肪酸、ポリアミノ、ポリエーテル、ポリエステル、ポリウレタン、ポリアクリレート等の相溶性鎖を有するコポリマーや共重合体等の各種分散剤が挙げられる。
　本組成物の固形分１００質量％に対する分散剤の配合量は、好ましくは０．１～１０質量％である。 <Dispersing agent>
A dispersing agent may be added to the present composition from the viewpoint of improving the dispersibility of the pigment (D) in the composition and easily forming a cured film having a good appearance.
The dispersant is not particularly limited, and, for example, a copolymer having a pigment-adsorbing group such as carboxylic acid, phosphoric acid or amine, a copolymer having a compatible chain such as fatty acid, polyamino, polyether, polyester, polyurethane or polyacrylate Various dispersants such as copolymers may be mentioned.
The compounding amount of the dispersant based on 100% by mass of the solid content of the present composition is preferably 0.1 to 10% by mass.
＜本組成物の用途＞
　本組成物は、様々な箇所に用いることができるが、本組成物を用いて形成される硬化被膜は、抗ウイルス性に優れ、かつ金属アレルギーを引き起こさないため、人と接する物（例：携帯電話、スマートフォン、タブレット等の画像表示装置を備える機器および家電等の電気製品、画像表示装置の保護フィルム、家具、ドアノブ、手すり、自動車のハンドル、おもちゃ）、人が存在する空間に存在する物（例：壁、床、天井、ドア、階段、窓ガラス等の内外装材、照明器具、自動車の内装材）などに好適に用いることができる。 <Use of the present composition>
Although this composition can be used in various places, the cured film formed using this composition is excellent in antiviral property and does not cause metal allergy, so it is in contact with human beings (eg, portable) Devices equipped with image display devices such as telephones, smartphones and tablets, electrical appliances such as home appliances, protective films for image display devices, furniture, doorknobs, handrails, handlebars of automobiles, toys) Example: It can be suitably used for walls, floors, ceilings, doors, stairs, interior and exterior materials such as window glass, lighting fixtures, interior materials of automobiles, and the like.
≪硬化被膜、硬化被膜付き基材≫
　本発明の一実施形態に係る硬化被膜（以下「本硬化被膜」ともいう。）は、前記本組成物から形成された膜であり、具体的には、本組成物を光照射により硬化させる工程（硬化工程）を含むことで製造することができる。
　また、本発明の一実施形態に係る硬化被膜付き基材は、基材と前記本硬化被膜とを含む。
　前記本硬化被膜および本硬化被膜付き基材は、具体的には、本組成物を基材の少なくとも一部に塗布する工程（塗布工程）と、その後、光照射により塗布された本組成物を硬化させる工程（硬化工程）とを含むことで製造することができる。 «Cured film, substrate with hardened film»
The cured film (hereinafter also referred to as "the main cured film") according to an embodiment of the present invention is a film formed from the present composition, and specifically, the step of curing the present composition by light irradiation It can manufacture by including (hardening process).
Moreover, the base material with a cured film which concerns on one Embodiment of this invention contains a base material and the said main cured film.
Specifically, the present cured film and the substrate with the present cured film specifically apply the present composition to at least a part of the substrate (coating step) and then apply the present composition by light irradiation. It can manufacture by including the process (hardening process) made to harden | cure.
＜基材＞
　基材としては、特に制限されず、前記本硬化被膜を形成したい被塗物であればよく、プラスチック、木材、金属、ガラス、セラミックス、コンクリート等を挙げることができる。プラスチックとしては、例えば、各種プラスチック基材（例：トリアセチルセルロース、ポリエチレンテレフタレート（ＰＥＴ）、ジアセチルセルロース、アセテートブチレートセルロース、ポリエーテルサルホン、ポリアクリル、ポリウレタン、ポリエステル、ポリカーボネート、ポリスルホン、ポリエーテル、ポリメチルペンテン、ポリエーテルケトン、（メタ）アクリルニトリル等から形成されるフィルムや成形体）が挙げられる。 <Base material>
The substrate is not particularly limited as long as it is a substrate on which the main cured film is to be formed, and examples thereof include plastics, woods, metals, glasses, ceramics, and concrete. Examples of the plastic include various plastic substrates (eg, triacetyl cellulose, polyethylene terephthalate (PET), diacetyl cellulose, acetate butyrate cellulose, polyether sulfone, polyacrylic, polyurethane, polyester, polycarbonate, polysulfone, polyether, Films and molded articles formed from polymethylpentene, polyether ketone, (meth) acrylonitrile and the like can be mentioned.
＜塗布工程＞
　前記塗布工程における塗布（コーティング）方法としては、用いる本組成物の組成および基材の種類等に応じて適時選択すればよいが、例えば、スプレーコート法、ディップコート法、エアーナイフコート法、カーテンコート法、ローラーコート法、ワイヤーバーコート法、グラビアコート法、エクストルージョンコート法、ディッピング法が挙げられる。 <Coating process>
The application (coating) method in the application step may be appropriately selected according to the composition of the present composition to be used, the type of the substrate, etc. For example, spray coating, dip coating, air knife coating, curtain Coating method, roller coating method, wire bar coating method, gravure coating method, extrusion coating method, dipping method can be mentioned.
　前記塗布工程の後、前記硬化工程の前に、塗布された組成物を乾燥させる乾燥工程を設けてもよい。この乾燥工程は、乾燥時間を短縮させるため、５～１２０℃程度の加熱下で行ってもよい。 After the application step, a drying step may be provided to dry the applied composition before the curing step. This drying step may be performed under heating at about 5 to 120 ° C. to shorten the drying time.
＜硬化工程＞
　前記硬化工程において照射される光としては、活性エネルギー線が好ましく、該活性エネルギー線としては、例えば、遠紫外線、紫外線、近紫外線、赤外線等の光線、Ｘ線、γ線などの電磁波、電子線、プロトン線、中性子線が挙げられ、これらの中でも、硬化速度、照射装置の入手のし易さ、価格などの点から、紫外線が好ましい。 <Hardening process>
The light irradiated in the curing step is preferably an active energy ray, and examples of the active energy ray include far ultraviolet rays, ultraviolet rays, near ultraviolet rays, rays such as infrared rays, electromagnetic waves such as X rays and γ rays, and electron rays And a proton beam and a neutron beam. Among these, ultraviolet rays are preferable in view of curing speed, availability of an irradiation apparatus, cost and the like.
　紫外線で硬化させる方法としては、２００～５００ｎｍの波長域の光を発する高圧水銀ランプ、メタルハライドランプ、キセノンランプ、ケミカルランプ、無電極ランプ、ＬＥＤランプ等を用いて、紫外線を照射量１００～３，０００ｍＪ／ｃｍ2程度で照射する方法等が挙げられる。 As a method of curing with ultraviolet light, the irradiation dose of ultraviolet light is 100 to 3, using a high pressure mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrode lamp, an LED lamp or the like that emits light in a wavelength range of 200 to 500 nm. The method etc. which are irradiated by about 000 mJ / cm < 2 > etc. are mentioned.
　前記硬化工程では、光を照射した後、または、光を照射する際に、硬化時間を短縮させるために、５～１２０℃程度の加熱を行ってもよい。 In the curing step, heating may be performed at about 5 to 120 ° C. in order to shorten the curing time after or during the light irradiation.
＜本硬化被膜の物性等＞
　本硬化被膜の厚さは、基材を保護できる程度の厚みであれば特に限定されないが、好ましくは１～１０μｍ、より好ましくは２～７μｍ、特に好ましくは２～５μｍである。 <Physical properties etc. of main cured film>
The thickness of the cured film is not particularly limited as long as it can protect the substrate, but it is preferably 1 to 10 μm, more preferably 2 to 7 μm, and particularly preferably 2 to 5 μm.
　本硬化被膜表面のＪＩＳ　Ｂ　０６０１：２０１３に基づいて測定した粗さ曲線要素の平均長さ（ＲＳｍ）は、好ましくは３００μｍ以下である。
　前記ＲＳｍが３００μｍ以下であると、抗ウイルス性により優れる硬化被膜を得ることができる傾向にある。 The average length (RSm) of the roughness curvilinear element measured based on JIS B 0601: 2013 of the main cured film surface is preferably 300 μm or less.
If the RSm is 300 μm or less, a cured film which is more excellent in antiviral property tends to be obtained.
≪ウイルス不活化方法≫
　本発明の一実施形態に係るウイルス不活化方法（以下「本方法」ともいう。）は、前記本硬化被膜または本硬化被膜付き基材を用いて、少なくとも暗所において、ウイルスを不活化する方法である。具体的には、本硬化被膜とウイルスとを接触させることで、ウイルスを不活化する。前記接触は、通常、常温下で行われるが、場合によっては加熱下で行ってもよい。具体的には、家電製品の筐体、スマートフォンのディスプレイ等の画像表示装置および保護フィルム、自動車の内装、自動車のウィンドウフィルム、壁、床、天井等の内装材、家具の表面等の物品に、本硬化被膜を形成し、硬化被膜に接触したウイルスを不活化する方法が挙げられる。本方法によれば、これらの物品が、室内、車庫、収納家具内および鞄の中等の暗所にある場合や夜間においても、ウイルスを不活化することができる。
　本方法は、インフルエンザウイルスを含む様々なＲＮＡウイルスの不活化に用いることができ、特に、インフルエンザウイルスの不活化に好ましく用いることができる。
　ウイルスを不活化できたか否かは、ＪＩＳ　Ｌ　１９２２：２０１６に準拠したウイルス活性値の値で確認できる。
　なお、本発明において、「暗所」とは、紫外光を含め、光の存在しない箇所のことをいう。 «Method of virus inactivation»
The virus inactivation method according to an embodiment of the present invention (hereinafter also referred to as "the present method") is a method of inactivating a virus at least in a dark place using the main cured film or the substrate with the main cured film. It is. Specifically, the virus is inactivated by bringing the cured film into contact with the virus. The contact is usually performed at normal temperature, but may be performed under heating in some cases. Specifically, for articles such as housings of home appliances, image display devices such as displays of smartphones and protective films, interiors of automobiles, window films of automobiles, interior materials such as walls, floors and ceilings, surfaces of furniture, etc. The method of forming this cured film and inactivating the virus which contacted the cured film is mentioned. According to this method, the virus can be inactivated even when these articles are in a dark place such as in a room, in a garage, in storage furniture and in a bag or at night.
This method can be used for inactivation of various RNA viruses including influenza virus, and in particular, can be preferably used for inactivation of influenza virus.
Whether or not the virus has been inactivated can be confirmed by the value of the virus activity value in accordance with JIS L 1922: 2016.
In the present invention, the "dark place" refers to a place where no light exists, including ultraviolet light.
　以下、実施例に基づいて本発明の好適な態様をさらに具体的に説明するが、本発明はこれらの実施例に限定されない。 Hereinafter, preferred embodiments of the present invention will be more specifically described based on examples, but the present invention is not limited to these examples.
［実施例１～６および比較例１～２］
　表１に示す配合で下記材料を混合することにより、光硬化性樹脂組成物を調製した。
　なお、表１における光硬化性樹脂組成物の欄の数値は、質量部を示し、固形分および固形分の密度は、用いた原料から算出した値である。 [Examples 1 to 6 and Comparative Examples 1 to 2]
A photocurable resin composition was prepared by mixing the following materials in the composition shown in Table 1.
In addition, the numerical value of the column of the photocurable resin composition in Table 1 shows a mass part, and the density of solid content and solid content is the value computed from the used raw material.
＜抗ウイルス剤（Ａ）＞
・酸性基含有高分子のナトリウム塩およびアルキルフェニルスルホン酸ナトリウムを含有する水分散体（固形分３５％） <Antiviral agent (A)>
・ Water dispersion containing sodium salt of acid group-containing polymer and sodium alkylphenyl sulfonate (solid content 35%)
＜光硬化性樹脂（Ｂ）＞
・「Ｌａｒｏｍｅｒ　ＵＡ９０４８」（ＢＡＳＦジャパン（株）製、６.５官能ウレタンアクリレート樹脂、密度：１．１６４ｇ／ｃｍ3）
・「アロニックス　Ｍ－８５６０」（東亞合成（株）製、ポリエステルアクリレート樹脂、密度：１．１３４ｇ／ｃｍ3） <Photocurable resin (B)>
・ "Laromer UA9048" (manufactured by BASF Japan Ltd., 6.5 functional urethane acrylate resin, density: 1.164 g / cm 3 )
・ "ALONIX M-8560" (manufactured by Toagosei Co., Ltd., polyester acrylate resin, density: 1.134 g / cm 3 )
＜不飽和単量体（Ｃ）＞
・「Ｌａｒｏｍｅｒ　ＴＰＧＤＡ」（ＢＡＳＦジャパン（株）製、トリプロピレングリコールジアクリレート、密度：１．０３０ｇ／ｃｍ3）
・「ビスコート　＃２６０」（大阪有機化学工業（株）製、１，９－ノナンジオールジアクリレート、密度：０．９８８ｇ／ｃｍ3）
・「ライトアクリレート　ＭＴＧ－Ａ」（共栄社化学（株）製、メトキシトリエチレングリコールアクリレート、密度：１．０６ｇ／ｃｍ3） <Unsaturated Monomer (C)>
-"Laromer TPGDA" (manufactured by BASF Japan Ltd., tripropylene glycol diacrylate, density: 1.030 g / cm 3 )
・ "Biscoat # 260" (Osaka Organic Chemical Industry Ltd., 1,9-nonanediol diacrylate, density: 0.988 g / cm 3 )
-"Light acrylate MTG-A" (manufactured by Kyoeisha Chemical Co., Ltd., methoxytriethylene glycol acrylate, density: 1.06 g / cm 3 )
＜顔料（Ｄ）＞
・「ミズカシル　Ｐ－８０２Ｙ」（水澤化学工業（株）製、シリカ、平均粒子径：５μｍ、密度：１．８７ｇ／ｃｍ3）
・「アートパール　ＡＫ－８００ＴＲ」（根上工業（株）製、ウレタンビーズ、平均粒子径：６μｍ、密度：１．２ｇ／ｃｍ3） <Pigment (D)>
"Mizukasyl P-802Y" (manufactured by Mizusawa Chemical Industries, Ltd., silica, average particle size: 5 μm, density: 1.87 g / cm 3 )
・ "Art Pearl AK-800TR" (Konae Industry Co., Ltd., urethane beads, average particle size: 6 μm, density: 1.2 g / cm 3 )
＜光重合開始剤（Ｅ）＞
・「イルガキュア　１８４」（ＢＡＳＦジャパン（株）製、１－ヒドロキシ－シクロヘキシル－フェニル－ケトン）
・「イルガキュア　ＴＰＯ」（ＢＡＳＦジャパン（株）製、２，４，６－トリメチルベンゾイル－ジフェニル－フォスフィンオキサイド）
・「イルガキュア　７５４」（ＢＡＳＦジャパン（株）製、オキシ－フェニル－アセチックアシッド２－[２－オキソ－２－フェニル－アセトキシ－エトキシ]－エチルエステルとオキシ－フェニル－アセチックアシッド２－[２－ヒドロキシ－エトキシ]－エチルエステルとの混合物）
・「イルガキュア　１２７」（ＢＡＳＦジャパン（株）製、２－ヒロドキシ－１－｛４－［４－（２－ヒドロキシ－２－メチル－プロピオニル）－ベンジル］フェニル｝－２－メチル－プロパン－１－オン） <Photoinitiator (E)>
・ “IRGACURE 184” (BASF Japan Ltd., 1-hydroxy-cyclohexyl-phenyl-ketone)
・ “Irgacure TPO” (BASF Japan Ltd., 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide)
・ “Irgacure 754” (manufactured by BASF Japan Ltd., oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester and oxy-phenyl-acetic acid 2- [2 Mixtures with -Hydroxy-ethoxy] -ethyl ester)
“IRGACURE 127” (manufactured by BASF Japan Ltd., 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propane-1-l on)
＜その他添加剤＞
・「ポリフロー　Ｎｏ．７５」（共栄社化学（株）製、アクリル系レベリング剤）
・「ＤｉｓｐｅｒＢＹＫ－２１６４」（ビックケミージャパン（株）製、分散剤） <Other additives>
・ "Poly flow No. 75" (Kyoeisha Chemical Co., Ltd. product, acrylic leveling agent)
・ "DisperBYK-2164" (manufactured by Bick Chemie Japan Co., Ltd., dispersant)
＜硬化被膜付き基材の作製＞
　東洋紡（株）製のＰＥＴフィルム「コスモシャインＡ４３００」に、前記調製した光硬化性樹脂組成物を乾燥膜厚が約３μｍとなるように１回塗布し、高圧水銀ランプにて紫外線を照射することで（照射量：４００ｍＪ／ｃｍ2）、塗膜を硬化させ、硬化被膜付き基材を得た。 <Preparation of a substrate with a cured film>
The photocurable resin composition prepared above is applied once to a PET film “Cosmo Shine A4300” manufactured by Toyobo Co., Ltd. so that the dry film thickness is about 3 μm, and the ultraviolet light is irradiated with a high pressure mercury lamp. (Irradiation dose: 400 mJ / cm 2 ), the coating was cured to obtain a substrate with a cured coating.
＜ウイルス活性値評価＞
　下記濃度のインフルエンザウイルス液を用い、シャーレ上で洗い出しおよび洗い出し液の回収を行った以外はＪＩＳ　Ｌ　１９２２：２０１６に準拠して、得られた硬化被膜付き基材のウイルス活性値（抗ウイルス性）を評価した。
　具体的には、硬化被膜付き基材および硬化被膜無し基材（対照試料）を６ｃｍ角に切り出してサンプルとし、前記サンプルをシャーレ内に置き、その表面にインフルエンザウイルス液（濃度：１０5～１０6ＰＦＵ／ｍＬ）を滴下し（反応面積４ｃｍ角）、暗所（２５℃）で２時間静置した。その後、シャーレ上でウイルス液を洗い出し液により回収し、希釈系列を作成した。前記希釈系列を上皮細胞（イヌ腎臓由来細胞）に感染させ、ＴＣＩＤ50測定法によってウイルス感染価を測定し、抗ウイルス活性値を求めた。
　抗ウイルス活性値が２．０以上のものを合格とし、３．０以上のものを特に優れていると評価した。結果を表１に示す。 <Evaluation of virus activity value>
Virus activity value of the substrate with a cured film obtained (antiviral) in accordance with JIS L 1922: 2016 except that the following concentration of influenza virus solution was used to wash out on a petri dish and recovery of the washout solution was performed Was evaluated.
Specifically, a substrate with a cured film and a substrate without a cured film (control sample) are cut into 6 cm square and used as a sample, and the sample is placed in a petri dish, and influenza virus liquid (concentration: 10 5 to 10) on the surface 6 PFU / mL) was added dropwise (reaction area 4 cm square), and allowed to stand in the dark (25 ° C.) for 2 hours. Thereafter, the virus solution was washed out on a petri dish and recovered by the solution to prepare a dilution series. Epithelial cells (dog kidney-derived cells) were infected with the dilution series, and the virus infectivity titer was measured by TCID 50 assay to determine the antiviral activity value.
Those having an antiviral activity value of 2.0 or more were taken as pass, and those having 3.0 or more were evaluated as particularly excellent. The results are shown in Table 1.
＜粗さ曲線要素の平均長さ（ＲＳｍ）の測定＞
　得られた硬化被膜付き基材を用い、該基材の硬化被膜表面の粗さ曲線要素の平均長さ（ＲＳｍ）を、ＪＩＳ　Ｂ　０６０１：２０１３に準拠し、表面粗さ形状測定器（ハンディサーフＥ－３５Ｂ、（株）東京精密製）を使用して測定した。結果を表１に示す。 <Measurement of average length (RSm) of roughness curve element>
Using the obtained substrate with a cured film, the average length (RSm) of the roughness curve element of the cured film surface of the substrate is in accordance with JIS B 0601: 2013, and a surface roughness shape measuring instrument (Handysurf E-35B, manufactured by Tokyo Seimitsu Co., Ltd.). The results are shown in Table 1.
＜抗ウイルス剤の分散性評価＞
　光硬化性樹脂組成物を、５０℃の環境下で１日静置した後、外観を確認し、抗ウイルス剤（Ａ）が組成物中に均一に分散している場合を合格（○）、組成物が２層以上に分離して沈殿が生じている場合を不合格（×）とした。結果を表１に示す。 <Evaluation of antiviral agent dispersibility>
After leaving the photocurable resin composition to stand for 1 day in an environment of 50 ° C., the appearance is confirmed, and the case where the antiviral agent (A) is uniformly dispersed in the composition is passed (○), The case where the composition was separated into two or more layers and precipitation occurred was regarded as rejection (x). The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001

Claims (9)

  1. 　酸性基含有化合物のアルカリ金属塩および酸性基含有化合物のアルカリ金属塩を含む重合体から選択される少なくとも１種を含む抗ウイルス剤（Ａ）と、光硬化性樹脂（Ｂ）と、不飽和単量体（Ｃ）と、顔料（Ｄ）と、光重合開始剤（Ｅ）とを含有する光硬化性樹脂組成物。 An antiviral agent (A) containing at least one selected from a polymer containing an alkali metal salt of an acid group-containing compound and an alkali metal salt of an acid group-containing compound, a photocurable resin (B), and an unsaturated single monomer The photocurable resin composition containing a monomer (C), a pigment (D), and a photoinitiator (E).
  2. 　前記顔料（Ｄ）が無機顔料を含有する、請求項１に記載の光硬化性樹脂組成物。 The photocurable resin composition according to claim 1, wherein the pigment (D) contains an inorganic pigment.
  3. 　前記顔料（Ｄ）の顔料容積濃度（ＰＶＣ）が２％以上である、請求項１または２に記載の光硬化性樹脂組成物。 The photocurable resin composition according to claim 1 or 2, wherein a pigment volume concentration (PVC) of the pigment (D) is 2% or more.
  4. 　請求項１～３のいずれか１項に記載の光硬化性樹脂組成物から形成された硬化被膜。 A cured film formed from the photocurable resin composition according to any one of claims 1 to 3.
  5. 　前記硬化被膜の、ＪＩＳ　Ｂ　０６０１：２０１３に基づいて測定した粗さ曲線要素の平均長さ（ＲＳｍ）が３００μｍ以下である、請求項４に記載の硬化被膜。 The cured film according to claim 4, wherein an average length (RSm) of a roughness curvilinear element measured based on JIS B 0601: 2013 of the cured film is 300 μm or less.
  6. 　基材と請求項４または５に記載の硬化被膜とを含む硬化被膜付き基材。 A substrate with a cured film comprising the substrate and the cured film according to claim 4 or 5.
  7. 　請求項１～３のいずれか１項に記載の光硬化性樹脂組成物を光照射により硬化させる硬化工程を有する硬化被膜の製造方法。 A method of producing a cured film comprising a curing step of curing the photocurable resin composition according to any one of claims 1 to 3 by light irradiation.
  8. 　請求項１～３のいずれか１項に記載の光硬化性樹脂組成物を基材の少なくとも一部に塗布する塗布工程と、
    　前記塗布工程の後、光照射により前記光硬化性樹脂組成物を硬化させて硬化被膜を形成する硬化工程と、
    を有する被膜付き基材の製造方法。     An application step of applying the photocurable resin composition according to any one of claims 1 to 3 to at least a part of a substrate;
    After the application step, a curing step of curing the photocurable resin composition by light irradiation to form a cured film;
    A method of producing a coated substrate having:
  9. 　請求項４もしくは５に記載の硬化被膜、または、請求項６に記載の硬化被膜付き基材を用いて、少なくとも暗所においてウイルスを不活化するウイルス不活化方法。 The virus inactivation method of inactivating a virus at least in the dark using the cured film according to claim 4 or 5 or the substrate with a cured film according to claim 6.
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